Chemical Sensors: Comprehensive Sensor Technologies. Volume 6: Chemical Sensors Applications Copyright © Momentum Press®, LLC, 2012 All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means—electronic, mechanical, photocopy, recording or any other— except for brief quotations, not to exceed 400 words, without the prior permission of the publisher. First published by Momentum Press®, LLC 222 East 46th Street, New York, NY 10017 ISBN-13: 978-1-60650-239-6 (hard back, case bound) ISBN-10: 1-60650-239-5 (hard back, case bound) ISBN-13: 978-1-60650-241-9 (e-book) ISBN-10: 1-60650-241-7 (e-book) DOI forthcoming Cover design by Jonathan Pennell Interior design by Derryfield Publishing, LLC 10 9 8 7 6 5 4 3 2 1 Printed in the United States of America

PREFACE TO CHEMICAL SENSORS: COMPREHENSIVE SENSOR TECHNOLOGIES PREFACE TO VOLUME 6: CHEMICAL SENSORS APPLICATIONS ABOUT THE EDITOR CONTRIBUTORS 1 CHEMICAL GAS MIXTURE ANALYSIS AND THE ELECTRONIC NOSE: CURRENT STATUS, FUTURE TRENDS G. Korotcenkov J. R. Stetter 1 Introduction 2 Modern Methods of Gas Recognition 2.1 Gas Chromatography 2.2 Mass Spectrometry 2.3 GC-MS Method 2.4 Ion Mobility Spectrometry 2.5 Near-Infrared Spectroscopy 2.6 Other Methods of Gas Identification and Quantification 3 The Electronic Nose: Approaches and Achievements 3.1 A Brief History of the Electronic Nose 3.2 Definition of an Electronic Nose 3.3 The Electronic Nose: Principles of Operation for Detection of Odors 3.4 Sizes and Features of Sensor Arrays 4 Signal Processing in Electronic Noses 4.1 Pattern Recognition Software 4.2 Comparison of Chemical Sensor Array Pattern Recognition Algorithms 4.3 Short View of the Process of Software Design for Portable Devices 4.4 Electronic Nose Calibration 5 Electronic Nose Fabrication 5.1 Electronic Nose Configuration xi xv xvii xix


1 2 2 3 6 6 8 9 9 9 12 12 13 15 16 21 21 22 23 23



5.2 Sensor Arrays 5.3 Sampling System 6 Benefits of Electronic Noses 7 Reasons Limiting Optimal Operation of Electronic Noses 8 Markets for Electronic Noses 9 Applications of Electronic Noses 10 Summary 11 Acknowledgments References 2 ELECTRONIC TONGUES: APPROACHES AND ACHIEVEMENTS F. Winquist 1 Introduction 1.1 Biomimetic Systems 1.2 The Concept of Electronic Tongues 1.3 A Short History of the Development of Electronic Tongues 2 Measurement Principles 2.1 Potentiometric Techniques 2.2 Voltammetric Techniques 2.3 Other Techniques 3 Signal Processing 4 Applications 4.1 Electronic Tongues Based on Potentiometry 4.2 Electronic Tongues Based on Voltammetry 4.3 Miniaturized Systems 4.4 Flow Injection Analysis 4.5 Hybrid Systems 4.6 Performance of Electronic Tongues Compared with Other Analytical Techniques 4.7 Surface Acoustic Waves, Impedance Measurements, and Optical Techniques 5 Some Practical Considerations 6 Commercialization 7 Conclusions 8 Acknowledgments 9 Nomenclature References

23 34 36 38 39 44 46 46 46 57 57 57 58 59 60 60 62 65 66 67 67 70 73 74 75 75 76 77 78 78 79 79 79



WIRELESS CHEMICAL SENSORS A. Flammini S. De Vito 1 Wireless Sensors: An Introduction 1.1 Smart Sensors: From Wired to Wireless Technologies 1.2 Wireless Sensor Architecture 1.3 Batteries, Power Harvesting, and Power Scavenging 1.4 Communication Protocol Stack 1.5 Interference, Coexistence, Security, Synchronization, Localization 1.6 Wireless Technologies 2 Wireless Chemical Sensing 2.1 Application Scenarios 2.2 Chemical Sensors Technologies and Wireless Chemical Sensing 2.3 Wireless Chemical Sensing Architectures 3 Acknowledgments References


87 88 91 93 95 99 100 105 105 108 111 121 121 127


REMOTE CHEMICAL SENSING: APPLICATION FOR ATMOSPHERE MONITORING Dong Jiang Yaohuan Huang Dafang Zhuang 1 Introduction 2 Techniques and Instruments for Atmosphere Monitoring 2.1 Techniques for Atmosphere Monitoring 2.2 Sensors for Atmosphere Monitoring 3 Applications 3.1 Aerosol Retrieval 3.2 Water Vapor Retrieval 3.3 Atmospheric Trace Gases Detecting 4 Conclusion References

127 128 128 130 136 136 137 139 143 143 147 147 148 148 156


CHEMICAL SENSORS IN OUR LIVES G. Harsanyi 1 Introduction 2 Biomedical Applications 2.1 Blood Control 2.2 Ion-Selective Sensor Applications


2.3 Measurement of Inhaled and Exhaled Gases 2.4 Sensors for Metabolites in Blood, Tissue, and Secretions 2.5 Humidity Sensors in Biomedical Applications 3 Water Quality Monitoring 3.1 Dissolved Oxygen and pH 3.2 Electrical Conductivity, Oxidation–Reduction Potential, Turbidity, and Salinity 3.3 Ionic Compounds 3.4 Oil and Other Organic Pollutants 3.5 Biological Oxygen Demand and Integral Water Quality 3.6 Dissolved Gases in Water (Chlorine, Ozone Water Treatment Monitoring) 4 Food Quality Monitoring 4.1 pH in Food and Beverages 4.2 Quality Control Tests (Meat Freshness, Milk Quality, Oil, and Fat) 4.3 Sensors for Food Process Control 4.4 Determination of the Variety of Foodstuffs and Manufactured Goods 5 Environmental Control 5.1 Atmosphere Monitoring (Air Pollution and Humidity Control) 5.2 Rain Composition Monitoring 5.3 Detection of Airborne Microbes 6 Household Applications 6.1 Climate Control 6.2 Home Safety (Gas Leakage, Fire Alarm) 6.3 Ventilation (Indoor Air Quality) Control 6.4 Multisensor Systems for Smart Homes 6.5 Control of Food Preparation 7 Nomenclature References 6 CHEMICAL SENSORS IN INDUSTRY, AGRICULTURE, AND TRANSPORTATION G. Harsanyi 1 Introduction 2 Automotive Applications 2.1 Sensors for Exhaust Control 2.2 Passenger Compartment Air Quality Sensors 2.3 Odor Sensors for Quality Control in the Automotive Industry 2.4 Oil Quality Sensors 3 Chemical Sensors in Industrial Processes 3.1 Industrial pH and Oxidation–Reduction Potential Sensors

158 162 166 166 167 170 171 176 179 180 184 184 187 189 193 196 196 203 204 205 206 207 208 210 211 212 213 221 221 222 222 229 232 232 235 235


3.2 3.3 3.4 3.5

Humidity Sensing in Industry Gases in Industry (Process Control, Leakage, and Workplace Safety) Combustion Control Other Applications

237 239 248 251 254 254 255 257 257 260 263 263 265 267 268 269 269 271 272 272 273 275 276 281

4 Fire Alarm Systems 4.1 Smoke Detection 4.2 Gas Sensors as Fire Detectors 5 Agricultural Applications 5.1 Ammonia Control in Animal Facilities 5.2 Soil Quality Control 6 Law Enforcement Applications 6.1 Drug Detection 6.2 Breath Analysis (Alcohol Testing) 6.3 Sensors Against Terrorism 7 Air and Space Applications 7.1 Detecting Hydrogen Leakage 7.2 Emissions Control 7.3 Spacecraft Air Quality 8 Military Applications 8.1 Detection of Landmines and Explosive Residues 8.2 Warfare Agent Detection 9 Nomenclature References 7 CHEMICAL SENSOR SELECTION AND OPERATION GUIDE G. Korotcenkov B. K. Cho 1 What Is an Ideal Chemical Sensor? 2 How the Field of Application Influences Our Conception of the Ideal Sensor 3 Chemical Sensors for Various Applications: What Determines the Choice? 4 Do Sensors with Low Selectivity Have a Future? 5 Future Trends 6 Some Practical Advice for Gas Sensor Selection and Use 6.1 Sensor Selection 6.2 Sensor Parameters 6.3 Sensor Calibration and Testing 6.4 Sensor Location 6.5 Sensor Installation

281 283 284 295 297 299 300 303 305 331 332


6.6 Sampling 6.7 Training 7 Summary 8 Acknowledgment References APPENDIX: BOOKS RELATED TO THE FIELD OF CHEMICAL SENSORS INDEX

333 339 339 340 340 349 367

In spite of their century-long history, chemical sensors appeared on the commercial market only 50 years ago. In recent years, however, the field of chemical sensors has broadened and expanded greatly. At present, chemical sensors are being used in medicine, agriculture, industry, transport, environmental control, and other fields. However, the process of developing new sensors as well as improving older types of chemical sensors is still ongoing. New technologies and the toughening of ecological standards require more sensitive instruments with faster response times, better selectivity, and improved stability. The second half of this six-volume series on chemical sensors, devoted to comprehensive sensor technologies, describes these developments and the new processes and applications. These volumes are intended to be a primary source for both fundamental and practical information about where sensor technologies are now and where they are headed for the future. We are sure that Volumes 4–6 in this series will be a useful addition to the first three volumes, on fundamentals of sensing materials, in which various sensing materials that can be used in chemical sensors are discussed in detail. Analysis of chemical sensor design, fabrication, and functioning requires other approaches to description in comparison with materials science problems, and therefore we decided that consideration of materials and devices should be carried out separately. From our point of view, dividing the series into two parts as we have done results in more logical narration and more utility for readers who are interested in different aspects of chemical sensor design. In this series we provide readers with a thorough understanding of the concepts behind chemical sensors, presenting the information necessary to develop such sensors, covering all aspects including fundamental theories, fabrication, functionalization, characterization, and real-world applications, so as to enable them to pursue their research and development requirements. Therefore, we hope that this series will help readers understand the present status of chemical sensors and will also act as an introduction, which may encourage further study, as well as an estimate of the roles that chemical sensors may play in the future. Chemical Sensors: Comprehensive Sensor Technologies is a three-volume series, comprising Volumes 4, 5, and 6 in our series, Chemical Sensors. Volume 4 deals with solid-state devices, Volume 5 with electrochemical and optical sensors, and Volume 6 with applications of chemical sensors. The chapters included in the volumes consist of review and overview papers written by experts in the field. The authors



of each of the chapters were chosen very carefully and are all well known throughout the world in their fields of study. Therefore, these books provide an up-to-date account of the present status of chemical sensors, from fundamental science and processing to applications. Specifically, Volume 4 includes descriptions of solid-state sensors such as conductometric or resistive gas sensors, Schottky-, FET-, capacitance-, and pyroelectric-type chemical sensors. Pellistors, mass-sensitive, and acoustic wave sensors are described as well. Integrated chemical sensors are also discussed in Volume 4. Volume 5 provides information related to electrochemical and optical sensors. Fundamentals of operation, methods of fabrication, and operating characteristics of electrochemical gas sensors, solid electrolyte–based gas sensors, ion-selective electrodes, CHEMFETs, and different types of optical, fiber optical, and chemoluminescence chemical sensors are discussed. Volume 6 is dedicated to detailed examination of opportunities for applications of chemical sensors in various areas of our lives, including medicine, industry, environmental control, agriculture, and transportation. It is the editor’s wish that theses volume will provide the reader with a detailed understanding of the many applications of chemical sensors in both today’s world and that of the future. In these chapters one can also find descriptions of architecture and fundamentals of “electronic noses” and “electronic tongues,” principles of wireless chemical sensor design, and possibilities for remote chemical sensing for atmospheric monitoring. In this three-volume series, the authors present sensors that utilize various sensing materials and phenomena. The terminology and concepts associated with sensors are presented, including some of the relevant physical and chemical phenomena applied in the sensor signal transduction system. As is well known, chemical sensing is multidisciplinary by nature. The role of sensing materials in such phenomena is also detailed. We need to note that the number of disciplines involved in the research and design of chemical sensors has increased dramatically. New knowledge and approaches are needed to achieve miniaturization, lower power consumption, and the ability to operate in complex environments for more selective, sensitive, and rapid determination of chemical and biological species. Compact analytical systems that have a sensor as one of the system components are becoming more important than individual sensors. Thus, in addition to traditional sensor approaches, a variety of new themes have been introduced to achieve the attractive goal of analyzing chemical species on the micro and nano scales. Therefore, throughout these books, numerous strategies for the fabrication and characterization of sensing materials and sensing structures which are employed in sensing applications are provided, and current approaches for chemical sensing are described. This series can be utilized as a text for researchers and engineers as well as graduate students who are either entering the field for the first time, or who are already conducting research in these areas but are willing to extend their knowledge of the field of chemical sensors. We hope that these volumes will also be of interest to undergraduate students in chemical engineering, electronics, environmental control, and medicine. These books have been written in a way that final-year and graduate university students in the fields of chemistry, physics, electronics, biology, biotechnology, mechanics, and bioengineering can easily comprehend. We believe that practicing engineers or project managers which would like to use chemical sensors but don’t know how to do so, and how to select optimal chemical sensors for specific applications, also will find useful information. It is necessary here to comment briefly on the coverage of the literature. During our work on this series we tried to cover the field more or less completely. However, we need to acknowledge that an


appreciable number of relevant papers may remain unknown to the authors. Regarding these, the editors and contributing authors express regret, not only to the authors of such works, but also to the readers of our books. Finally, we wish to thank all those who participated in the preparation of this series, including the contributing authors and copyright owners in Europe, the United States, Asia, and the rest of the world. We also wish to express our gratitude to the staff of Momentum Press, and in particular Joel Stein, for his kind assistance in bringing these volumes to fruition.

Ghenadii Korotcenkov

The market for chemical sensors continues to grow at a rapid rate, reflecting the wide range of possibilities for improving technological processes in industry and agriculture as well as living conditions that can be enhanced by the use of chemical sensors. The military, medicine, air/space, and security markets also continue to drive research and development in this area. At present it is hard to imagine an area where chemical sensors would be useless. On the contrary, we note that every day new areas arise in which new analytical instrumentation with modern functional opportunities is urgently needed. It is necessary to admit, however, that the development of commercially successful chemical sensors is expensive and technically difficult, and also requires sophisticated market knowledge. This volume provides that knowledge. Just a list of some of the topics discussed—such as biomedical applications, water quality monitoring, food quality monitoring, environmental control, household applications, automotive applications, industrial processes, fire alarm systems, agricultural applications, law enforcement applications, air/space applications, military applications, etc.—provides a clear idea of the extensive analysis presented here, and how broad a perspective of the emerging sensor industry may be acquired. Proper attention in this book is given to consideration of the principles and construction of “electronic noses” and “electronic tongues.” As is becoming widely recognized, the ability to design such devices represents a huge achievement by designers of chemical sensors. Wireless sensors and remote chemical sensing, which are also discussed in this volume, constitute another trend in chemical sensors design, focused on building systems for global and local environmental monitoring. Nowadays, as our ecosystem is changing so rapidly and human-caused disasters occur more often, establishing such monitoring has become a priority. Researchers, development engineers, and students can use this volume as a reference source during their work and study according to their interests. We hope that this book and the series as a whole will help all those concerned with sensor research, development, and application to succeed in this promising field. The volume contains comparisons and assessments of the various types of sensors with respect to their practical applications. Therefore, the users of chemical sensors will also benefit. We believe that readers of this book will be able to do the following: • • Estimate the area of possible applications of chemical sensors. Know the advantages and disadvantages of various different types of chemical sensors.



• • •

Understand the special requirements for sensors used in specific applications. Estimate the reliability of chemical sensors. Determine which sensor types are most appropriate for a given application.

Ghenadii Korotcenkov


Ghenadii Korotcenkov received his Ph.D. in Physics and Technology of Semiconductor Materials and Devices in 1976, and his Habilitate Degree (Dr.Sci.) in Physics and Mathematics of Semiconductors and Dielectrics in 1990. For a long time he was a leader of the scientific Gas Sensor Group and manager of various national and international scientific and engineering projects carried out in the Laboratory of Micro- and Optoelectronics, Technical University of Moldova. Currently, he is a research professor at Gwangju Institute of Science and Technology, Gwangju, Republic of Korea. Specialists from the former Soviet Union know G. Korotcenkov’s research results in the study of Schottky barriers, MOS structures, native oxides, and photoreceivers based on Group III–V compounds very well. His current research interests include materials science and surface science, focused on metal oxides and solid-state gas sensor design. He is the author of eight books and special publications, 11 review papers, 10 book chapters, and more than 180 peer-reviewed articles. He holds 18 patents. He has presented more than 200 reports at national and international conferences. His articles are cited more than 150 times per year. His research activities have been honored by the Award of the Supreme Council of Science and Advanced Technology of the Republic of Moldova (2004), The Prize of the Presidents of Academies of Sciences of Ukraine, Belarus and Moldova (2003), the Senior Research Excellence Award of Technical University of Moldova (2001, 2003, 2005), a Fellowship from the International Research Exchange Board (1998), and the National Youth Prize of the Republic of Moldova (1980), among others.



Beongki Cho (Chapter 7) Department of Material Science and Engineering and Department of Nanobio Materials and Electronics Gwangju Institute of Science and Technology Gwangju 500-712, Republic of Korea Zhuang Dafang (Chapter 4) Data Center for Resources and Environmental Sciences State Key Lab for Resources and Environmental Information Systems Institute of Geographical Sciences and Natural Resources Research Chinese Academy of Sciences Beijing 100101, China Saverio De Vito (Chapter 3) Renewable Energy and Environment Advanced Physical Technologies Department ENEA—Italian Institute for New Technologies 1-80055 Portici (NA), Italy Jiang Dong (Chapter 4) Data Center for Resources and Environmental Sciences State Key Lab for Resources and Environmental Information Systems Institute of Geographical Sciences and Natural Resources Research Chinese Academy of Sciences Beijing 100101, China Alessandra Flammini (Chapter 3) Department of Electronics for Automation University of Brescia 38-25123 Brescia, Italy



Gábor Harsányi (Chapters 5 and 6) Department of Electronics Technology Budapest University of Technology and Economics 1521 Budapest, Hungary Ghenadii Korotcenkov (Chapters 1 and 7) Department of Material Science and Engineering Gwangju Institute of Science and Technology Gwangju 500-712, Republic of Korea and Technical University of Moldova Chisinau 2001, Republic of Moldova Joseph R. Stetter (Chapter 1) KWJ Engineering, Inc. Newark, California 94560, USA Fredrik Winquist (Chapter 2) The Swedish Sensor Centre and the Division of Applied Physics Department of Physics and Measurement Technology Linköping University SE-581 83 Linköping, Sweden Huang Yaohuan (Chapter 4) Data Center for Resources and Environmental Sciences State Key Lab for Resources and Environmental Information Systems Institute of Geographical Sciences and Natural Resources Research Chinese Academy of Sciences Beijing 100101, China



G. Korotcenkov J. R. Stetter 1. INTRODUCTION
Today’s chemical sensors do not have high selectivity, making it difficult to determine the nature of gas molecules in the atmosphere. At the same time this task in many cases is a determining one, in that identification of molecules can provide information necessary for identification of the source of either toxic gases or odor. The sense of smell is one of the most important senses for human beings, often controlling behavior. For example, the perception of volatile compounds by the human nose is of great importance in evaluating the quality of foods and cosmetics, and thus can enrich our daily lives. Sensory analysis by a panel of experts is a costly process for industries, because it requires trained people who can work for only relatively short periods of time. Therefore, scientists have long been thinking about elaboration of an electronic analog of the human nose—an electronic nose or e-nose—that would not be subjective in evaluation and would have a long life. The task of odor identification is a complicated one. Odors can be complex mixtures of many hundreds of chemical species, and often even subtle changes in the relative amounts of even one of these species can be detected as a change in the odor. The concentration of those odorant molecules may be



as low as a few parts per trillion. We are learning more about the process of olfaction and about odorant molecules, many of which are apparently low-molecular-weight molecules that are partly hydrophobic and sometimes have one polar group, frequently containing an oxygen, nitrogen, or sulfur moiety (Strike et al. 1999).

There are many methods for analysis of gases that provide both qualitative and quantitative results. These methods involve obtaining and using multidimensional data. In this section we survey common techniques that have, at least at one time, been called electronic noses. Descriptions of those methods can be found in books and reviews such as those of Kaplan and Braham (1998), Pearce et al. (2003), and Rock et al. (2008).

Gas chromatography (GC) is an old and well-accepted technique for the measurement and identification of gases. Simple descriptions (Kaplan and Braham 1998) include a common type of gas chromatographic equipment consisting of a small capillary tube with an interior diameter of about 25–250 m and a length of 1–30 m (see Figure 1.1). The inside wall of the hollow tube (the column) is coated with a thin polymeric film, of from onetenth to a few micrometers thick. As odorants are transported down the tube by the mobile phase (gas), the film, or stationary phase, interacts with the mixture, selectively impeding the progress of each of the components of the mixture toward the outlet. The interaction of the analytes and film depends on the physical and chemical properties of the gas, such as the boiling point, the polarity, hydrogen bonding, polarizability, etc., and the affinity of each single substance for the stationary-phase film material.

Figure 1.1. Essential parts of a micro-gas chromatograph, which can be built on a single substrate and can be called a micro total analytical system (μTAS).


Therefore, the transport time of each of the various molecular constituents of the mixture vary with their vapor pressure and/or solubility, causing them to emerge from the column outlet separately. One can think of the process as an auto race in which all the contestants begin at the same time in a group, but stretch out and arrive in single file at the finish line. The partitioning behavior in gas/solid and gas/ liquid chromatography has been well studied for many film materials and many gas mixtures and can be found in basic textbooks on analytical chemistry (Strobel and Heineman 1989; Willard et al. 1988; Skoog et al. 2007). While there are many choices for detectors for the eluting components at the end of the column, a gas sensor can often be used to generate a peak-shaped current response with the emergence of each of the constituent gases. The height and the area of the peaks is a measure of the amount of each of the odorant constituents in the carrier gas. While the most common sensor for hydrocarbons is a flame ionization detector, in which a flame heats a small gap between two wires such that each constituent gas produces an electrical current as it passes through the flame, many detectors have been used, both simple ones such as amperometric gas sensors (Stetter 1986) and complex ones such as mass spectrometers (Strobel and Heineman 1989). The GC method is a batch process and not continuous but, while typically taking some minutes to accomplish, can be completed in less than a second for some mixtures (Eiceman et al. 2006). For any selected chromatographic method, the batch analysis can be optimized by selection of optimum operational parameters including the carrier gas flow rate, an increase of the temperature-program heating rates, a reduction of the column length, and/or a reduction of the thickness of the stationary phase (Rock et al. 2008). Depending on the sample, it is important to avoid using all possibilities at once, because this always results in a decrease of resolution, sample capacity, or both. It is also important to note that these optimizations increase the demands on the detector technology used in terms of sensitivity, speed, and dead volume. Recent developments in GC instrumentation, using the latest technologies for fabrication of the chromatographic column, have considerably shortened the time needed for analysis .

Mass spectrometry (MS) is another method which can be used for identification of a gas or gas mixture (Richardson 2000; Schalley 2001; Mano and Gato 2003; Vinaixa et al. 2004). The first instruments of an e-nose type that were based on MS were developed at the end of the 1990s (Dittmann et al. 1998). Some researchers do not consider the MS system used in this manner as an e-nose (Mielle et al. 2000) and prefer to leave the MS detector in its classical role in analytical science, while others report these instruments as ‘‘mass sensors’’ or ‘‘new-generation electronic noses’’ (Peres et al. 2003). It is a bit of semantics, but MS has been used, like GC, with pattern recognition for identification of gas mixtures in a parallel fashion to the sensor array–based e-nose. The mass spectrometer contains an inlet, ionization chamber, accelerator, mass filter, and ion detector in a vacuum and represents a process for separation and subsequent detection of molecules or atoms. In MS, each constituent compound molecule is ionized, typically by electron beam (electron ionization) or through interaction with reagent ions (chemical ionization), and the energy absorbed by


Figure 1.2. Average mass spectrum of a gasoline sample. (Reprinted with permission from Perez Pavon et al. 2006. Copyright 2006 Elsevier.)

the molecule in effect breaks it into fragments (Peres et al. 2000; Dittmann and Nitz 2000). In general, the total abundance of the mass fragments and the discriminating power of the mass spectra increase with the ionization energy level. However, the energy level that yields the best signal-to-noise ratios depends on the material being studied (Begnaud and Berdagu 2002). Ionized fragments are injected into a mass filter that separates them according to their mass-to-charge ratio (m/z) (see Figure 1.2), yielding a quantitative abundance measurement of each ion of different mass. The mass separation takes place within an electric and/or magnetic field, and nowadays a variety of mass analyzers are well established. There are many types of mass analyzers, such as double-focusing magnetic and electric sensors, quadrouple mass filters, quadrupole ion traps, time-of-flight mass spectrometers, and Fourier-transform ion cyclotron resonance mass spectrometers, all capable of performing these measurement. The choice of mass analyzer is dictated largely by the goal of the research, based on the required mass range, mass accuracy, resolution, sensitivity, cost, and dynamic range (Mano and Gato 2003). Finally, the ions are collected at the electron multiplier, and the current is measured. The spectrum resulting from simultaneous ionization and fragmentation of the mixture of molecules introduced constitutes a ‘fingerprint’’ that is characteristic of the original sample being analyzed. Exploitation of this spectral information allows determination of the composition of the sample to some extent (Peres et al. 2003; Perez Pavon et al. 2006). The mass spectrum obtained results from the simultaneous ionization and fragmentation of all the volatile compounds present in the sample. The selection of particular fragment ions may be based on knowledge of the headspace composition—analytical chemistry can provide the necessary tools to characterize the samples—or on the results of mathematical feature extraction. Thus, information about what kinds of molecules are responsible for the differences between samples can be obtained from the ion fragmentation patterns. In some cases, the mass spectrum that results can be used to identify the original molecular composition. These results can then be compared directly with results obtained using conventional GC-MS instruments and more formal analytical methods for validation. The sensitivity


and the selectivity of such an instrument can sometimes be improved using MS in the selected ion monitoring (SIM) mode. One example of a mass spectrometer used as an electronic nose is shown in Figure 1.3. This instrument is simply a direct-injection quadrupole mass spectrometer; it is a conventional analytical instrument, but with reconfigured software to make the output look like an e-nose system. The performance of this type of e-nose is attractive because the technology is mature, the limit of detection is down to the parts-per-billion level, and there is practically no interference from ambient conditions, e.g., humidity, or airborne pollutants such as CO. There is no doubt that MS-based systems can have considerable advantages over simple sensor arrays because of their inherent direct measurement of a molecular property (the mass-to-charge ratio of a molecule), the response to a broad range of species of interest, and the high sensitivity of ion-based analytical techniques. Advantages of MS over conventional sensor arrays include fewer problems of poisoning, less chance of profile masking by some major constituents of the sample (e.g., ethanol), no strong influence of moisture, and no nonlinearity of signals (Perez Pavon et al. 2006). Of course, the system cost and complexity can be substantially greater than that of a simple chemical sensor array. However, MS is also inherently a very fast technique, and all the compounds can be introduced into the mass spectrometer rapidly and simultaneously, with no chromatographic separation necessary. Despite the great potential of the MS-based e-noses in the field of food analysis, there are still some aspects of the technique that need to be improved. Signal instability is one of the problems of MS-based e-noses that has not yet been solved. It causes the mass spectrum of a sample to change when the same sample is analyzed some days later. Many factors contribute to signal instability, and the cause may lie in the MS itself (e.g., gradual fouling of the ion source, vacuum instability, aging of the ion multiplier, or change of a filament). This instability is a common problem in the analytical application of the e-nose technique and requires an additional set of samples (i.e., standards) to be analyzed at regular intervals.

Figure 1.3. The Gerstel ChemSensor 4440 manufactured by Gerstel GmbH & Co. KG with participation of Agilent Technologies is a type of quasi-electronic nose based on an automated headspace sampler and an MS. (Uploaded from


While this approach to analysis (comparison of the unknown to a standard) is the most acceptable for e-noses today, management of the reference samples (selection, physical and chemical stability, and storage), especially in food analysis or other complex tasks, often presents a major problem.

The combination of gas chromatography followed by mass spectrometry has become the gold standard for compositional analysis of complex mixtures and is constantly being improved (Lavine 1992; Kaplan and Braham 1998; Aishima 2004; Berna et al. 2008; Capelli et al. 2008). The powerful analytical separation of constituents in time followed by mass spectroscopy of each eluant from the column provides the most data for pattern-recognition analysis. In brief, the GC column separates an odorant mixture into its molecular constituents, and the MS generates a mass spectrum for each peak. The spectra are typically compared to spectra in a large chemical database to help identify the specific chemical compound in each constituent peak. The spectrum of labeled peaks, together with the concentration information and the elution time from the gas chromatographic column, is then used to distinguish the odorant mixture in the original samples. The mass spectrum, with its fragmentation patterns, provides unique fingerprints for discriminating the molecular identity in a sample and between samples. Applications of these instruments to date have included measurement of volatile food components, identification of “off” fragrances, and detection of rancidity in edible oils.

A major limitation to the field use of mass spectrometry is the need for a vacuum pump, as there are as yet no simple, small, low-cost vacuum pumps for MS. Ion mobility spectrometry (IMS) is an ionization technique with many similarities to MS but operates at ambient pressure and therefore has no need for a vacuum pump. The operating principle of IMS is similar to that of MS in that there is a sample inlet, ionization chamber, time-of-flight (TOF) drift region in which the ions are separated, and an ion detector (Figure 1.4). The major difference in IMS is that, the ions are not separated by the difference in the mass/charge ratio, but rather on the basis of their different ion mobilities in the drift gas (Vakhrushev et al. 2008). Ion mobility depends not just on mass/charge but also on the reduced mass, charge, and the different collision cross sections as determined by the ion’s size and shape, all of which directly influence the separation observed. During the process of sampling, ionization, separation, and detection, there are many collisions between the ions and the drift gas (often dry air) molecules, because the measurement is performed at ambient pressure (Creaser et al. 2004). While the most common agent for ionization is a radioactive alpha emitter such as 63Ni or 241Am, there have recently been many developments relating to nonradioactive, low-cost and low-power ionization sources. Typically, a series of ion–molecule reactions takes place in the ionization source, and often a sample molecule with high proton affinity reacts in air with a trace amount of H2O and undergoes a proton transfer reaction to a positively charged ion by collision with the ionized water (the ionized water is called the reactant ion and is always present in the source, to chemically ionize the target analyte). By


Figure 1.4. Schematic diagram of an ion mobility spectrometer. Ions are generated in an ionization region by any number of methods from plasma and electrospray to a 63Ni source. An ion shutter or electronic method pulses the ions into the drift tube region, where they are accelerated by a uniform weak electric field toward a detector. Their progress is impeded by a number of collisions with the drift gas and each other. Larger ions with greater collision cross sections experience more collisions. Therefore, the separation of ions of differing shape and size becomes possible. (Reprinted with permission from Creaser et al. 2004. Copyright 2004 The Royal Society of Chemistry.)

doping the drift gas with NH3 vapor, acetone, chlorinated solvents, or other chemicals, the nature of the reactant ion is changed and then the selectivity in the ion source can be modified. Injection of the ions into the drift region can be controlled electronically such that, using differing polarities for the drift region, either positive or negative ions can be analyzed. Substances with electroncapturing capabilities, such as halogenated compounds, can be detected in the negative-ion mode, while positive ions are analyzed in the positive-ion mode (the detector is at a negative potential relative to the ion source). Another often-used ionization alternative, for compounds with sufficiently low ionization potential, is UV photoionization. This is appropriate for selective measurements of molecules with ionization potentials of less than 11.4 eV. After ionization of the air sample, the ions are pulsed through a shutter into a drift tube, which is isolated from atmospheric air. The drift tube has a uniform and relatively weak electric field of about 200 V/cm, which accelerates the ions along the drift region. The movement is hindered by collisions, and the ion typically reaches its “ion mobility” or maximum drift velocity in the field until the ions reach the detector at the end. There have been some new methods of injecting the ions to simplify the shutter grid cell design, but in general the drift takes up to about 200 ms. When the ions approach the detector a shutter grid is used to avoid unwanted charging effects. When the ions finally strike the detector, a current is generated and is measured along with the time of flight. For a manageable and calibrated component amount, this gives information about the identity and concentration of the analyte. When the sample composition is complex, however, there can be many ion–ion interactions, ion–drift gas interactions, or overlapping peaks, complicating interpretation


of IMS spectra and lowering resolution. In many of these cases, the classical electronic nose approach using data-evaluation algorithms (Massart et al. 1988) can be applied to gain a maximum of information from the confounding measurements. Compared to mass spectrometry, the virtual sensor array (many signal channels produced by the IM spectra over time) is not interpretable by discrete mass/charge relationship as in MS, but by the signal integration over definable time intervals to produce patterns that are related to the chemistry of the complex separation produced in the IMS. In this way, the IMS data reflects the sample chemistry and the IMS is operated like the e-nose devices.

Infrared (IR) spectroscopy can also be used with pattern recognition and a sampling system and therefore can be considered as an electronic nose (MacDonalds and Prebbleis 1993; Blanco and Villarroya 2002; Van Kempen et al. 2002; Cozzolino et al. 2003; Armenta et al. 2006; Rock et al. 2008). The nearinfrared (NIR) spectral region is generally defined as the range between 800 and 2500 nm. In this range, molecular vibrations and higher energy levels are excited (see Figure 1.5). Through characteristic absorption bands, the type of chemical bonds can be determined, and pure chemicals can be identified by their unique fingerprint spectra. The spectra of mixtures is evaluated by classical electronic nose algorithms. Spectral features in the NIR region are overtones and combinations of vibrations observed in the mid-infrared (IR) region and are therefore much less intense (10- to l000-fold), broader, and more overlapping than the parent absorptions. The consequently greater difficulty of assigning NIR absorptions to structural features may be a disadvantage, but this is compensated by other aspects: Unique combination

Second overtone H2O ROH RNH2 CH CH2 CH3 1100 1500

First overtone H2O RCOOH

Combinations H2O ROH RNH2

CH CH CH3 2000 Wavelength, nm

CH CH2 CH3 2500

Figure 1.5. Overtones and combinations in the NIR spectral region. (Reprinted with permission from MacDonalds and Prebbleis 1993. Copyright 1993 Elsevier.)


bands offer information that is not available in the mid-IR, the reduced intensities allow direct measurements on undiluted samples, and measurements of, or in the presence of, water are readily performed (MacDonalds and Prebbleis 1993). A more detailed description and analysis of the advantages and disadvantages of NIR spectroscopy are given by Blanco and Villarroya (2002) and Anderson et al. (2005). For the detection of substances in the gas phase, two affordable methods for use in portable devices are known. In photo-acoustic infrared spectroscopy, a modulation of the intensity of an IR source causes a temperature variation and a resulting expansion and contraction of the gas that is measured at audible frequencies with a microphone. Alternatively, the absorbed energy of a narrow-bandpass infrared beam is measured in filter-based IR spectroscopy. Commercially available nondispersive infrared (NDIR) instruments (e.g., MIRAN SapphIRe from Thermo Scientific) are used mostly for absolute measurements of concentration, either for detection of a single species which has a unique absorbance wavelength or by analysis at multiple wavelengths for a known gas mixture. However, when the constituents of the gas mixture are unknown, these instruments can be combined with pattern recognition and also used as an electronic nose. In spite of the confirmed feasibility (Van Kempen et al. 2002), the infrared-based e-nose has not become popular, and commercially available devices such as the MIRAN SapphIRe from Thermo Scientific can rather be considered as portable analytic tools and not electronic noses.

Other analytical methods can also be used for gas recognition. For example, pulse spectroscopy, a technique patented by Bloodhound Sensors, uses a single solid-state sensor which interacts directly with volatile compounds to give a spectroscopic trace similar to fingerprint mass spectrometry (Chandler et al. 1997). The method has the advantages that it is extremely rapid, with full response times of the order of seconds, and sample processing is minimal. It is also amenable to miniaturization, potentially enabling instrumentation to become hand-held in the future while providing the discriminating power of mass spectrometry.

In spite of the incontestable advantages of the methods so far considered, instrumental methods of determining odors such as gas chromatography and mass spectrometry are expensive and require trained personnel. Moreover, chromatography is a batch process and can take a relatively long time (minutes to hours) in spite of recent improvements in millisecond-timescale GC. Further, the size, cost, and performance of these analytical instruments still does not allow for a low-cost, portable electronic nose. Therefore, there is still a need for devices for rapid, inexpensive analysis of volatile organic compounds (VOCs) which does not require specialist technicians. Ideally, field devices should be portable,


allowing direct online or offsite measurements. As analytical instruments, these systems must be designed for long-term use with high repeatability (the ability to obtain the same pattern for a sample on the same array over short intervals of time) and reproducibility (the ability of different sensor batches or different instruments to produce the same pattern for the same sample) (Schaller et al. 1998). Of course, they also should be capable of continuous measurements in various environments. The first successful attempts to elaborate such devices were made in the 1980s and 1990s. In particular, in 1982, Persaud and Dodd first reported experiments with three- and four-sensor arrays in an effort to imitate human olfaction. At the same time, a sensor array instrument complete with a patternrecognition algorithm and an automatic sampling system was developed by Stetter et al. (1985b) (see Figure 1.6). This device, patented by Argonne National Laboratory (ANL) scientists, won an IR-100 award and awards for the inventors from the U.S. Department of Energy. The term electronic nose or e-nose was first suggested by Julian Gardner of Warwick University in 1988 (Gardner, 1988) and came into popular use after a 1989 NATO conference on the subject. Since then, development of sensor array–based instruments has been actively pursued in Asia, North America, and Europe. Using instruments based on sensor arrays, the low selectivity of many types of chemical sensors can sometimes be resolved, though at the cost of using an array of reversible but only semiselective detection layers with different chemical properties. An e-nose has been defined as “an instrument which

Figure 1.6. View of the fully automated portable Chemical Parameter Spectrometer sensor array (CPS-100 sniffer) designed at Argonne National Laboratory and demonstrated during 1980–1983. The sensor array included four sensors operated in four modes. (Reproduced with permission from the Electrochemistry Encyclopedia,


comprises an array of electronic chemical sensors with partial specificity and an appropriate pattern recognition system, capable of recognizing simple or complex odours” (Gardner and Bartlett 1994). There are also other, similar definitions in the literature (Stetter and Penrose 2001). The sensor arrays feed responses (usually transduced to electronic impulses) into specialized computer software which produces multidimensional response profiles that can be thought of as a digital “smellprint” or “fingerprint” that represents the chemical complexity of the gas mixture. In the first e-nose device designed by Persaud and Dodd (1982), they used three different metal oxide gas sensors and identified among 20 odorous substances, including essential oils and pure volatile chemicals by the steady-state signals of these sensors. In the work of Stetter et al. (1985), the device identified more than 100 different chemicals. Pattern classification was performed by visual comparison of ratios of sensor responses by Persaud and Dodd (1982), while statistical pattern recognition was coupled to the e-nose in the ANL device (Zaromb and Stetter 1984; Stetter et al. 1986). Focusing primarily on the sensor aspect of the problem, the initial research of Persaud and Dodd only explored the use of metal oxide devices while the ANL device consisted of thermal catalytic sensors and electrochemical sensors to form a heterogenous sensor array. Later work at Warwick University explored the use of conducting polymers, while the work at ANL explored additional sensors and time-dependent responses (Stetter 1986; Zaromb et al. 1986; Stetter and Otagawa 1987). In applications, the ultimate selectivity of chemical sensors is achieved by using multiple sensors in an array, by using different sensors in the array, by modulating the sensors (i.e., using different operating protocols), and by the application of pattern-recognition techniques to interpret responses obtained from the sensor array. Using sensor arrays, we begin to appreciate the analytical power of a collection of sensors which are exposed to the same or nearly the same sample, and their responses are interpreted together. Research on chemical sensor arrays/electronic noses has progressed in Europe, North America, and Asia since the early 1980s, and there has been a series of international conferences on the subject (see, e.g., Stetter and Penrose 2001b, 2002). The research on sensor arrays and the resulting instruments that were introduced were made possible by many advances in science and technology, including improved sensors and improved microprocessors, and in pattern recognition and chemometrics that were being developed in analytical chemistry primarily for understanding structure–activity relationships. Early reports of “sniffers” and research on odorants include those of Wilkens and Hatman (1964), who reported on redox reactions of odorants at an electrode; Buck et al. (1995), who discussed the modulation of conductivity by odorants; and Dravieks and Trotter (1965), who reported the modulation of contact potential by odorants. There have been attempts to obtain multidimensional sensor signals from a single sensor such that one can make an electronic nose using a single sensor. These approaches use either a dynamic working mode for the sensor or simultaneous measurement of several parameters by one sensor. This allows multiple signals characterizing the state of the gas sensing material. For example, in various works (Stetter and Otagawa 1987; Stetter et al. 1989, 1990, 1991; Vaihinger et al. 1991; Nakata et al. 2002), a sinusoidal temperature perturbation was applied to a semiconductor gas sensor and the resulting conductance of the sensor was analyzed. It was found that the sensor response changes in a characteristic way depending on the composition of the gaseous mixtures and can be characterized by fast Fourier transformation (FFT). Others (Takada 1998; Heilig et al. 1999) showed that combined utilization of the temperature drop and the resistance changes of a single SnO2- or In2O3-based sensor provided a new possibility for


gas identification and determination of gas concentration. Recently, the modulation of microelectromechanical systems (MEMS) HMOX sensors has resulted in an array of micromachined sensors (Taylor and Semancik 2002; Wheeler et al. 2007). Temperature-programmed sensing for gas recognition has also been proposed (Meier et al. 2007). None of these approaches, however, found appropriate expansion and commercialization because of the lower reliability of the results obtained when analyzing complicated gas mixtures. Therefore, in this chapter we focus our attention only on electronic noses elaborated on the basis of sensor arrays.

As we mentioned before Gardner and Bartlett (1994) defined the electronic nose as “an instrument, which comprises an array of electronic chemical sensors with partial specificity and an appropriate pattern-recognition system, capable of recognizing simple or complex odours.” This seems very far from the human nose, and according to Mielle et al. (1995, 1996), such an analytical system is “obviously electronic but not a nose.” In fact, the only aspect in common with our odor-sensing organ is its function. Like the mammalian nose, it detects gases by means of sensors which send signals to a recognition organ—that is, to the brain or to a computer. The operating principle, the number of sensors, as well as the sensitivity and selectivity, are, however, very different (Bartlett et al. 1997). This is why some scientists prefer to call this instrument by other names, for example, “flavour sensor,” “aroma sensor” (Mielle 1996), “odour sensing system” (Gardner and Bartlett 1994), “multi-sensor array technology” (Shiers 1995; Mielle and Marquis 2000), or “chemical parameter spectrometer” (Stetter et al. 1984). Recent attempts to more closely mimic the mammalian (dog, rat, mouse) nose have been reviewed (Stetter 2010), and the use of mammalian odor receptors in sensors is showing promising utility (Persaud et al. 2005).

There are two types of odors: simple odors that tend to arise from single light, polar compounds, such as citral (lemon) or benzaldehyde (bitter almond); and complex odors that comprise hundreds or thousands of different compounds, such as the headspace of coffee or tea. Electronic noses are designed to be able to detect both these odor types (Varanda and Gardner 1999). The general principle of the e-nose technique is that the volatile compounds in the headspace of the sample are introduced into a detection system, where the volatile compounds interact with an array of gas sensors. Then, for each sample analyzed, the detector generates a set of signals that contains information about the volatile composition of the sample. Fundamental to the artificial nose is the idea that each sensor in the array has different sensitivity (Craven et al. 1996; Gardner 2004). Selectivity is maximized when each gas sensor responds more selectively to a certain chemical parameter or chemical quality (such as the polarity, polarizability, or electrochemical redox potential) of chemical compounds such that the array is able to image in “chemical” space. This can lead to multiple responses on multiple sensors in the array for compounds that have some polar character as well as some polarizability or hydrogen-bonding character; compounds with


differing amounts of these chemical properties produce unique fingerprints, and the sensors show crossreactivity or partial selectivity. For example, Odorant No. 1 may produce a high response in one sensor and lower responses in others, whereas Odorant No. 2 might produce high readings for sensor 2 and lower on other sensors. So, each sensor in the array has a unique response profile to different odorants under test. This means that the pattern of response across the sensors is distinct for different odorants. In this way, a small number of gas sensors (usually 3–32) can respond to a variety of different complex odors and there is no need to have one specific sensor for each individual compound. This ability to distinguish chemical identity is a unique property of the sensor array over an individual sensor signal and allows the system to identify an unknown odor from the pattern of sensor responses. When several samples are analyzed, a data matrix is generated that can constitute a “library” of known responses. The matrix of data can be subsequently treated with chemometric techniques so that the unknown samples can be compared to the library on the basis of their multiple responses (i.e., chemical composition), and classified. This approach allows analysis not just of intensity or quantity but a classification of the odor based on its origin, variety, purity, ripeness, aging, or any other complex property of interest. This technique sometimes does not provide information on the amounts of the individual aroma compounds; rather, it makes a global, qualitative estimation of the aroma profile and can sometimes offer an indication of odor intensity based on the intensity of the odor fingerprint. In this respect, it is similar to human olfactory perception. So, the output of the electronic nose may be the identity of the odorant, an estimate of the concentration of the odorant, or the characteristic properties of the odor as might be perceived by a human. When statistical techniques are used, it should be borne in mind that results will be reliable only if a significant number of samples of the different categories of the property of interest are analyzed and kept in the library for comparison. Figure 1.7 shows a simple schematic layout of an electronic nose and the main elements of the artificial olfactory system.

Discussions of an electronic nose should include addressing the issue of how many sensors should be included in an array. The most direct way to improve the data would seem to be to increase the number of sensors of the same type, e.g., use 20 or 40 sensors instead of four. The theoretical sensitivity of an optical array of identical redundant sensors has been shown to increase as the square root of the number of sensors, as expected from simple Gaussian error theory (Dickinson et al. 1999). This means that there is a clear benefit to more sensors if they are completely and perfectly redundant. However, this approach meets rapidly diminishing returns (Stetter et al. 1986). Combining all types of available sensors in the many different modes of operation can lead to the incredible diversity that can be produced with sensor arrays. However, it has been found that too many sensors that are not exactly the same but that are also not independently responsive or orthogonal can add noise but no new signal information, and thus can actually reduce the differentiating power of an array (Stetter et al. 1986; Mitrovics et al. 1998). Moreover, an increase in the number of sensors in an array sharply increases the time necessary for processing data obtained from the sensor array. The potential information content of an array of signals is quite large even for a small sensor array (Gopel, 1998; Zellers et al. 1995, 1998). For example, for electrical fires, it was found that one can tell the type of fire as well as the stage of the fire

Raw Feature vector Odor class Post-processed odor class

Normalized measurements

Sensor array

Feature extraction Classification Decision making
Knowledge base Train Test

Sensor 1 Sensor processor Sensor processor Sensor processor Array processor

Sensor processor

Sensor 2

Sensor 3

PR engine


Sensor 4

• • •

Sensor n Signal processor

Sensor processor Pattern recognition engine

Sensor array

Figure 1.7. Diagram illustrating the functioning of electronic nose. (Adapted with permission from Gardner and Bartlett 1994. Copyright 1994 Elsevier; and Kaplan and Braham 1998. Copyright 1998 IEEE.)


using a subset of three sensors (one electrochemical and two heated metal oxide) in a single array (Ni et al. 2008). Therefore, it is possible that in many cases smaller arrays can have more capabilities than large arrays: All arrays are not created equal. The best arrays are designed for the intended purpose and separate the molecules or molecular mixture by their chemical compositional differences in terms of the sensory responses. The better method of selecting sensors for a sensor-based electronic nose is not to use as many different sensors as are available, but to select them with an eye to the desired application and with knowledge of the requirements for the analytical data. That is the only way to ensure that the substances which are to be detected are causing the signal (Rock et al. 2008) and that the signals can be differentiated from each other and from the background matrix variations. There is an optimum number of sensors for each application, although that number and the choice of sensors may differ greatly from one application to another. For example, a statistical approach illustrates that a small array of six sensors is all that is required to differentiate up to 100 different patterns/compounds (Zaromb and Stetter 1984). In real e-nose instruments the number of elements in sensor arrays is varied from 4 to 32, but for any instrumentation, the simpler the design, the lower will be the cost and the higher the reliability. Finally, research has shown that it is also necessary to take into account the mutual influence of sensors on each other. For example, it is often necessary to specify the order of the sensors in the array as well as the kinds of sensors. This is because some sensors act on the sample and change it. An example of this is metal oxide sensors, which efficiently oxidize the sample and change the response of other, downstream sensors or combustible gas sensors that consume a portion of the sample signal (Stetter et al. 1985a).

After the sensor array, the second most important component of an electronic nose is the pattern classifier (Shaffer et al. 1999; Jurs et al. 2000). This is a means of extracting information from the collected sensor array patterns by comparing or associating them. In practice, this means associating a pattern from an unknown sample with a set of patterns from known standards to determine the closest match, for the purpose of identification. According to Shaffer et al. (1999), an ideal pattern recognition algorithm should have the following six qualities: 1. High accuracy. For application of the chemical sensor system to field measurements, the pattern recognition algorithm must accurately classify new sensor signals (i.e., it should have a low falsealarm rate and, ideally, no missed detections). For military applications, such as the detection of toxic chemical vapors, classification rates of >90% accuracy are necessary. 2. Fast. For real-time analysis, the pattern recognition algorithm must be able to produce a classification quickly. Thus, algorithms that are computationally intense may not be appropriate for this application. 3. Simple to train. The classification rules used by the pattern recognition algorithm must be learned quickly. For many applications, the database of training patterns will need to be updated periodically, thus requiring the algorithm to “relearn” its classification rules. This procedure must be performed as simply and quickly as possible.


4. Low memory requirements. For field-portable sensor systems, the pattern recognition algorithm will be embedded in a microcontroller that usually has limited memory resources. Thus, pattern recognition algorithms with large memory requirements may not be appropriate for this application. 5. Robust to outliers. For chemical sensor array applications in uncontrolled environments, the pattern recognition algorithm must be able to reduce the potential for false alarms by being able to differentiate between sensor signals it was trained on and those on which it was not. The underlying assumption is that the algorithm has been trained to recognize all the important compounds. Thus, any new or ambiguous sensor signal (e.g., a chemical vapor which it has not been trained to recognize) should be ignored. 6. Produce a measure of uncertainty. For many applications of chemical sensor array systems, the pattern recognition algorithm must be able to produce a statistical measure concerning the certainty of the classification. For sensor applications, such as toxic vapor monitoring, such a measure will aid in reducing the occurrence of false alarms by requiring that the sensor system be >80% or 90% certain of a classification decision before a warning is given or an alarm sounded.

There are many tools available for the analysis of data from an array of chemical sensors (Jurs et al. 2000). Earlier, the vast majority of systems reported for electronic noses (including virtually all of the commercially available instruments) were based on steady-state measurements. Sensors were allowed to reach equilibrium and, after a predetermined time, the signal intensities from each sensor were measured. The resulting response vectors were time-independent and represented the absolute change in sensor signal with a measured odor (Dickinson et al. 1998). Early reports of using time-dependent responses (Zaromb et al. 1986) illustrated that inclusion of slow and fast response categories for sensor responses improved the ability to identify different molecular composition of chemical samples. Recently, the use of temporal data has begun to be explored for odor discrimination (White et al. 1996). This approach more closely parallels the presentation of odors to olfactory cells by the process of sniffing. Saunders et al. (1995) observed that the shapes of the time-dependent responses from piezoelectric crystal sensors were less variable than the maximum frequency changes induced by odorants. In addition to the potential for improving reproducibility, the use of temporal data has been shown to enhance analyte identification and quantification. The dynamic sensor signal depends on several physical parameters, such as the speed of the flow that carries the odor from the source to the sensor array, the chemical nature of the odor itself, the diffusion and reaction of the odor within the active sensing material, and the ambient conditions such as pressure, temperature, and humidity (Tan et al. 2001). Sophisticated software is necessary to be able to handle such complex information. In general, such software is based on powerful algorithms for pattern recognition. Research into pattern classifiers has been perhaps the most aggressively pursued aspect of electronic nose research. A large body of previous research on pattern classification and recognition has been used in the quest to extract the maximum information from the chemical data produced by the sensors (Pearce et al. 2003; Pardo et al. 2005; Snopok and Kruglenko 2005; Di Natale et al. 2006).


The first step in data analysis is to preprocess the signals generated by the multidimensional sensors (Martı et al. 2005). This process transforms the data into their most appropriate form and enhances the features within the data that are useful in the subsequent steps. The preprocessing steps include normalization, baseline correction, and noise reduction or variable weighing, among others. Many of these techniques have been used in MS and GC for many years. Afterwards, preprocessed data are analyzed by various chemometric techniques (Gardner and Bartlett 1992; Holmberg 1997; Schaller et al. 1998; Keller 1999; Pearce et al. 2003; Barbri et al. 2007), some of which are available in statistical software packages that are available separately or are included in instruments that produce multidimensional data arrays.

4.1.1. Statistical Analysis Techniques
According to Schaller et al. (1998), commercially available techniques fall into three main categories: 1. Graphical analyses: bar chart, profile, polar, and offset polar plots 2. Multivariate analyses: principal components analysis, canonical discriminant analysis, feature weighting, and cluster analysis 3. Network analyses: artificial neural network and radial basis function The choice of method depends on available data and the type of result that is required. GRAPHICAL ANALYSIS
Graphical analysis is the simplest form of data treatment that may be used with an electronic nose. This option is suitable when visually comparing samples to a single specified reference. However, when several references are used, analysis becomes more complicated and an alternative approach may be necessary. MULTIVARIATE ANALYSIS
Multivariate data analysis generally involves a process for data reduction; it reduces high dimensionality in a multivariate data set or problem in which variables are partly correlated (e.g., sensors with overlapping sensitivities), allowing the information to be displayed in a smaller dimension (typically two or three) (Gardner and Bartlett 1992; Fukunaga et al. 1995). Statistical methods of multivariate analyses used in electronic noses for pattern recognition include principal components analysis (PCA), canonical discriminant analysis (CDA), discriminant factorial analysis (DFA), feature weighting analysis (FW), and cluster analysis (CA) (Schaller et al. 1998). Principal component analysis is commonly used to analyze the responses of an artificial nose to both simple and complex odors (Dickinson et al. 1998). In this method, response vectors are broken down into their individual components and expressed as linear combinations of orthogonal vectors (Gardner 1991). By convention, the components are numbered in decreasing order of importance. In


practice, the majority of variance (and thus information for discrimination) is generally contained in the first two or three orthogonal vectors, owing to the high degree of co-linearity usually found in electronic nose data. Decomposing complex responses into their principal components provides a useful way to display sensory data because it allows a multicomponent dataset to be displayed as a two- or threedimensional chart (Figure 1.8). Cluster analysis provides a convenient way to isolate clusters or groups of response vectors by calculating the dissimilarity between each vector (dissimilarity being determined by representing each response as a point in multidimensional space and calculating the Euclidean distance between them). Discriminant factorial analysis is a multivariate technique which determines a set of variables which best discriminates one group of objects from another. The first instrumental electronic

Figure 1.8. Examples of responses from eight-sensor array: (a) a bar graph; (b) a polar plot; (c) results of PCA analysis. (Reprinted with permission from Dickenson et al. 1998. Copyright 1998 Elsevier.)


nose complete with pattern recognition used a K-nearest neighbor (KNN) algorithm to compare unknown vectors determined by the instrument to libraries of known compounds (Stetter et al. 1985b). In addition to the techniques mentioned above, one can also use multivariate pattern recognition techniques, such as linear discriminant analysis (LDA), soft independent modeling of class analogy (SIMCA), and partial least squares (PLS) regression to analyz output signals from an electronic nose. In particular, PLS regression, currently the most powerful multivariate calibration technique, has been recognized as an indispensable regression technique among analysts working in spectroscopy, chromatography, and sensory sciences (Martens and Naes 1989; Aishima 2004). ARTIFICIAL NEURAL NETWORK
For situations in which quantification or multicomponent mixture classification is desired, a more powerful, nonlinear prediction tool is required. The use of artificial neural networks (ANNs) is such an alternative for analyzing nonlinear e-nose data. A neural network consists of a set of interconnected processing algorithms functioning in parallel. On a very simplified and abstract level, ANNs are based on the cognitive process of the human brain. Mathematical functions, or neurones, link together to build a network, which mimics the human nervous system (Newman 1991). A weight is randomly assigned to each neurone and then adjusted by means of an iterative or “learning” process, for example, error backpropagation, until the desired outputs are obtained. The resulting set of weights and functions is then saved as a “neural network.” There are many variations of this approach, with a three-layer feed-forward network being the most widely employed architecture for handling e-nose data (Dickinson et al. 1998). Unlike other pattern recognition methods, a neural network is a dynamic, self-adapting system that can modify its response to external forces using previous experience, offering a more flexible and, due to the parallelism, faster method of analysis. In addition, it may more closely mimic mammalian neurone processing of odor stimuli (Newman 1991; Persaud and Pelosi 1992). A well-trained ANN is very efficient in comparing unknown samples to a number of known references. A direct comparison of statistical and ANN techniques carried out by Findlay et al. (1993) for the detection of biological activity in grain illustrates that the ANN can be more robust and tolerant to noise and errors than statistical pattern recognition. More recently, algorithms have been developed to process signals from sensor arrays dynamically (Tan et al. 2001). These dynamic processing techniques include traditional parametric and nonparametric methods as used traditionally in the field of system identification, as well as linear filters, time-series neural networks. In addition to being able to cope with the dynamic nature of the response of the sensor array, such dynamic signal processing techniques are also particularly suited to handle factors such as sensor drift. SUPERVISED/UNSUPERVISED
The pattern recognition methods of multivariate analysis can be divided into unsupervised or untrained techniques, and supervised or trained techniques. Unsupervised learning methods are generally used in exploratory data analysis, because they attempt to identify a gas mixture without prior information


about the nature of the samples. These techniques, which include PCA, CA, and multidimensional scaling, are useful when no example of different sample groups is available, or when hidden relationships between samples or variables are suspected (Gardner and Bartlett 1992). Conversely, supervised learning techniques classify an odor by developing a mathematical model relating training data, i.e., samples with known properties, to a set of given descriptors. Test samples are then evaluated against a knowledge base, and predicted class membership is deduced. These methods enable the system to reduce parameters other than volatile, for example, temperature and humidity, and train a system to look only at particular combinations of sensors to measure a given odor. ANNs as well as statistical techniques can be divided into supervised and unsupervised approaches. Supervised algorithms used in electronic noses include back-propagation-trained feed-forward networks (Rumelhart et al. 1986), learning vector quantizers, and Fuzzy ARTMAPs (Carpenter et al. 1992). Fuzzy ARTMAP is a self-organizing and self-stabilizing supervised classifier that shows generally superior performance in training compared with multilayer perception (MLP) (Carpenter et al. 1992, 1995). This method needs a minimum of known data to train the system correctly. If the number of available data is not sufficient, an erratic result will be obtained. An unsupervised ANN algorithm does not require predetermined odor classes for training and essentially performs clustering of the data into similar groups based on the measured attributes or features that serve as inputs to the algorithm. Unsupervised ANNs used in electronic noses include self-organizing maps (SOMs) (Kohonen 1989) and adaptive resonance theory networks. Generally, electronic nose data are best processed using trained techniques such as CDA, FW, ANN, or RBF (Schaller et al. 1998). LINEAR/NONLINEAR
The above multivariate analyses are all linear pattern recognition methods in which a model is calculated using linear combinations of input data (Holmberg 1997). Therefore, when the instrumental responses recorded are linear, as in MS-based e-noses, all the aforementioned statistical methods give very good results. However, in gas sensor–based e-noses, instrumental responses are essentially nonlinear. In such cases, input data must be transformed into linear responses before applying the chemometric techniques described above. For example, the use of preprocessing algorithms, such as averaging, linearization, or normalization, can improve the performance of these analytical techniques (Gardner and Bartlett 1992; Persaud and Pelosi 1992; Gopel 1995). Such an approach works well if a low concentration of volatiles ensures an approximately linear response. When high concentrations of volatiles are measured, a nonlinear pattern recognition technique, such as ANN or RBF, may be more appropriate. Nonlinear models usually need more parameters, since some of them are used to describe the shape of the nonlinearity (i.e., they have more input data than linear models). The main advantage of these methods is flexibility, i.e., the ability to adjust to more complex data variations. However, caution is necessary when choosing model flexibility; this can be achieved by selecting the number of parameters. If too many parameters are taken into account, the calculated model will be overly flexible, fitting to all relevant data variations and unwanted sensor noise. The best method to avoid an over-fitted model is to use training data to build a nonlinear model, and validation data to test this model (cross-validation) (Holmberg 1997).


Table 1.1. Qualitative comparison of pattern recognition algorithms PATTERN







Slow Fast Fast Fast Fast Slow Fast

Yes Yes Yes Sometimes No Yes Sometimes

High Low Low Low Low High Low

Yes Yes Sometimes Yes Sometimes Yes Yes

Possible Yes Yes Yes Possible Yes Possible

NN, nearest-neighbor pattern recognition algorithm; MLDA, Mahalanobis linear discriminant analysis; BLDA, Bayesian linear discriminant analysis; SIMCA, soft independent modeling of class analogy; BP-ANN, back-propagation artificial neural networks; PNN, probabilistic neural networks; LVQ, learning vector quantization. Source: Reprinted with permission from Shaffer et al. 1999. Copyright 1999 Elsevier.

Unfortunately, no pattern recognition algorithm is able to fully meet each of these requirements. Results of comparison study of chemical sensor array pattern recognition algorithms carried out by Shaffer et al. (1999) are presented in Table 1.1. Comparisons were made based on five qualitative criteria (speed, training difficulty, memory requirements, robustness to outliers, and the ability to produce a measure of uncertainty) and one quantitative criterion (classification accuracy). For these purposes four sample datasets, involving simulated data and polymer-coated surface acoustic wave chemical sensor array data, were used. Based on this analysis, Shaffer et al. (1999) made the following conclusions. Among the seven algorithms in this study and the four datasets, the neural network–based algorithms (LVQ, PNN, and BP-ANN) had the highest classification accuracies. This conclusion will not surprise anyone in the chemical sensor community. When considering the qualitative criteria, the LVQ and PNN approaches fared well compared to BP-ANN due to their simpler training methods. Shaffer et al. (1999) therefore recommendd the LVQ for most applications of chemical sensor arrays and the PNN for special cases where a confidence measure and fast training are critical, while speed and memory requirements are not.

As discussed earlier, the usual definition of an electronic nose states that the instrument includes nonspecific sensors plus a pattern recognition system. When designing the intelligent processing and smart


operation components of an electronic nose, several approaches, ranging from powerful desktop systems to portable systems with limited computational resources, may be considered, depending on the required instrument size and final application. According to Perera et al. (2002), when designing embedded pattern analysis software, it is important to keep in mind that the complexity of training (or estimation) algorithms tends to be much higher than the complexity of the algorithms in the operation phase. A typical example is principal component regression, in which simple matrix manipulation is needed in the operation phase, but more complex routines such as singular value decomposition (SVD) may be needed during model estimation. For platforms with limited computing power, some algorithms should be trained offline, usually in a host computer, and parameters delivered to the system using appropriate digital communications. For more powerful platforms, the same instrument will be able to adapt its data processing scheme to the problem of interest. If some learning engine has to be implemented in a portable device, computational resources are an issue to be taken into account in the system design, since there will be limitations in speed and often in memory. In developing the e-nose software, some knowledge must also be considered as to the hardware solution (i.e., if dynamic memory is available) (Perera et al. 2002). In any case, to maximize software portability between different platforms, we advocate for a modular system that can be customized at compilation time. This will allow the solution to become portable among different architectures in a range of instrument designs for an e-nose manufacturer. Perera et al. (2002) believe that the use of embedded technology provides several interesting benefits: availability of an abstraction layer for signal acquisition and control via an operating system, highlevel programming of the signal processing algorithms, large data storage in solid-state disks, commercial off-the-shelf hardware for Internet connectivity, I2C and CAN buses, serial ports, hardware for interfacing various types of displays, etc. Furthermore, an impressive trend toward reducing the cost and size of these systems can be observed in the marketplace.

Any analytical system made of sensors requires calibration. In the case of an e-nose, this can be response magnitude and relative magnitude for an array of chemical responses. Therefore, in order to develop the ability to recognize each chemical, the e-nose must be trained as well as calibrated. This task is very important for proper operation and successful application. In the training of an e-nose, the instrument is exposed repeatedly to varying concentrations of known compounds in varied order, and the resulting patterns of signals across the sensor array are stored and used in a computer algorithm. When consistent circulation of vapors through the e-nose for the vapors of the various calibration substances is complete, a library of responses is formed that is kept in the memory of the processor in the e-nose. This database of labeled signatures is used to train the pattern recognition system. The goal of this training process is to configure the recognition system to produce unique classifications of each chemical so that an automated rapid identification can be implemented in applications. Identification is made through comparison of the response of sample gas to responses obtained with authentic known substances, preprogrammed into the library of responses. Close matches to the library compounds is used to indicate the presence of specific substances or mixtures of molecules. The e-nose can also be trained


to recognize partial patterns caused by substances for which it has not been specifically trained—enough to identify the chemical’s functional groups. The most important limitation is that the e-nose does not often provide the molecular identity or molecular analysis for the odor. However, it is a powerful tool for comparative analysis and can identify subtle differences in extremely complex molecular mixtures.

Each e-nose can be divided into three or four basic modules. According to Tan et al. (2001), e-noses are comprised of four basic elements: a sampling system, which includes pumps, air conditioner, and flow controller; an array of sensors; an electronic data acquisition and control system; and pattern recognition software. At the same time, Marti et al. (2005) believe that an e-nose is a union of three elements: the sample-handling system; the detection system; and, last but by no means least, the data analysis system. In any case, one has to have hardware and software to accomplish the sampling, analysis, and reporting of the appropriate analytical information.

5.2. SENSOR ARRAYS 5.2.1. Sensors Acceptable for Application in Electronic Noses
The ideal sensors to be integrated in an electronic nose should fulfill the following criteria (Demarne and Sanjine 1992; Mari and Barbi 1992; Bartlett et al. 1993; Hodgins 1995, 1997; Schaller et al. 1998; Gardner 2004): high sensitivity toward chemical compounds, that is, similar to that of the human nose; low sensitivity toward humidity and temperature; medium selectivity, i.e., they must respond to different compounds present in the headspace of the sample; high stability; high reproducibility and reliability; robustness and durability; easy calibration; easily processable data output; and small dimensions. Fast response is also often desirable and, if a portable e-nose is wanted, the ideal sensors also should have low power requirements. This is a tall order, and sensors can fall short of this mark. The best sensor for the e-nose in this regard may be the mass spectrometer, but then the ideals of small size, low cost, and low maintenance are not realized easily. The most common sensors used in e-noses come from those used for industrial purposes and therefore have the many advantages of commercial practicality. Even if the sensors respond rapidly, like a MS, analysis times of e-nose systems are generally influenced more by the sampling method utilized than by the sensor response time. For example, some static sampling techniques require over 1 h for a sample reading, while some dynamic systems using similar sensors require less than 20 s. An average of around 5–10 min is common (James et al. 2005). As we noted earlier, for correct detection of a wide range of chemicals and complex mixtures, chemical sensors in the sensor array must have different sensitivities to the target analyte gases and to the matrix gases. Therefore, a sensor array should include a combination of several sensors of different basic type or of sensors of the same type but with different response characteristics. Sensor arrays that have


many of the same class of sensor but different types are said to be homogeneous arrays, and those that contain different classes of sensors and different types in each class are said to be heterogeneous arrays. However, it is necessary to note that the majority of electronic noses, commercial and otherwise, use sensors of the same class (homogeneous array), but generally of different types within a class. There are several different sensor transducer principles that allow us to divide sensors into classes, including electrochemical (e.g., amperometric and potentiometric), thermal (catalytic combustible gas sensors, calorimetric), mechanical (surface acoustic wave, quartz crystal microbalance, cantilever), optical (fiber optic evanescent wave, absorption), and electronic (chemiresistor, chemicapacitor). And there are many types of each class of sensor and many variations even within a type of sensor platform. This leads to a wide variety of sensors and tuning possibilities for operation in an array (James et al. 2005). Some authors use a simpler approach to classification (Mielle 1996). They divide all sensors for e-nose application into two broad groups: 1. “Hot sensors” (mainly the semiconducting metal oxide gas sensors) 2. “Cold sensors” (conducting polymers, bulk acoustic wave, and surface acoustic wave sensors). Comparative performance of sensors from these two groups of currently available sensors is summarized in Table 1.2. The heated metal oxide (HMOX) sensor is one of the most commonly used sensors in the field of electronic noses. For these sensors, different sensitive layers of different morphology with different doping, different production processes, different electrodes, different filter layers, and different operating

Table 1.2. Comparative properties of “cold” and “hot” sensors PROPERTY Power consumption Response time Selectivity Carrier gas Availability Lifetime Price “COLD” SENSORS Low (a few μW) Slow (20–40 s) Good (SAW and BAW sensors can be enanitioselective) May be inert (avoiding oxidation of sample) Commercially available (poor reproducibility) Not guaranteed to be more than 12 months (typically 18 months) Expensive “HOT” SENSORS High (50–800 mW) Fast (0.5 s to a few s) Poor (different for each type; can be adjusted by temperature modulation) Synthetic air (must contain O2) Commercially available (over 70 types; many providers) More than 5 years in normal use Low for single sensors; medium for arrays

SAW, surface acoustic wave; BAW, bulk acoustic wave. Source: Adapted from Mielle 1996.


temperatures all lead to different sensor responses. For example, Figaro Engineering, Inc., lists more than 25 tin oxide sensors in its product line, making a large variety of arrays possible using just this one type of chemiresistor sensor. The same diversity is found for other transducer principles, whether surface or bulk acoustic wave (SAW, BAW) sensors, metal oxide field-effect transistors (MOSFETs), electrochemical sensors, or conducting polymer (CP) sensors. The particular choice of sensors depends on the individual application (Albert et al. 2000). Advice on choice of sensors is generally provided by the manufacturer. The selection of chemical sensor types to be utilized is of utmost importance if e-nose classifications are to be useful for a wide range of applications or for a specific problem endpoint determination. Most manufacturers seek highly selective sensors, but often, in the case of an electronic nose, every compound present in the gaseous phase should be detected and therefore needs to find a response on at least one sensor. If a new compound is added to a mixture, at least one sensor must detect this addition in order for the sensor array to have an effect beyond simple dilution.

5.2.2. Sensor Array Fabrication
Any sensor that responds reversibly to a chemical in the gas or vapor phase may be suitable for use in an electronic nose instrument. This means that many principles of detection can be used for fabrication of sensor arrays for electronic noses. However, in all cases, the goal is to create an array of differentially sensitive sensing elements. One can find general information about sensor arrays in several good reviews (Albert et al. 2000; Stetter and Penrose 2001; James et al. 2005; Rock et al. 2008). In spite of the presence of many classes of sensors, the commercial e-nose is dominated by only a few types of sensors, including HMOX, MOSFETs, conducting organic polymers (CPs), piezoelectric crystals (SAW or BAW), amperometric gas sensors (AGS), and electrochemical sensors. Such sensors can be divided into two main classes: hot (HMOX, MOSFETs) and cold (CP, SAW, BAW, and AGS). The former operate at high temperatures and are considered to be less sensitive to moisture with less carryover from one measurement to another, but there is high variability in the reactivity and quality of these sensors. Other sensor types, such as fiber optic (Dickinson et al. 1996; Sutter and Jups 1997), electrochemical (Mari and Barbi 1992), and calorimetric (Gall 1993; Lerchner et al. 2000), also can be used and may be integrated into electronic noses. Whatever type of sensor is used, its limitations as well as advantages will be reflected in the resulting instrumentation. It is important to consider such instrumental performance parameters as sensitivity, detection limit, selectivity, transient response time, reproducibility, stability, and lifetime before choosing sensors, and to remember that these qualities are, basically, properties of the sensor’s chemically sensitive detection layer (Albert et al. 2000; Snopok and Kruglenko 2002). As can be seen in Figure 1.9, there are two main approaches to design of sensors arrays. Examples of sensors arrays fabricated using the indicated approaches are shown in Figure 1.10. Of course, the second approach is the more progressive one. Another very interesting approach to gas sensor microarray fabrication was developed at the Forschungszentrum Karlsruhe (Ehrmann et al. 2000). Figure 1.11 shows that, contrary to conventional macroarrays and also other gas sensor microsystems, a single monolithic metal oxide film alone forms


A) Conventional macro-structure
1 2 3 4
Separately housed sensors with different operating characteristics, mounted on large substrate

B) Microarray with separate sensor
1 2 3 4
Separate thin-film layers. Sensors differentiation by different sensing materials

Figure 1.9. Main approaches used for sensor array fabrication.

the basis of the whole array. This film is separated into sensor segments by parallel electrode strips to measure the electrical conductivity of the segments. A simple gradient technique differentiates the gas detection selectivity of the individual sensor segments. The thickness of an ultrathin gas-permeable membrane layer deposited on top of the metal oxide film varies across the array. Additionally, a controlled temperature gradient is maintained across the array by four platinum heating meanders located on the rear side of the chip. As both thickness and temperature have a gas-dependent influence on the diffusion through the membrane and the temperature influence on the gas reaction at the metal oxide interface also depends on the nature of the gases, gas detection selectivity is gradually modified from sensor segment to sensor segment. Therefore, the exposures to single gases or gas ensembles (such as

Figure 1.10. Examples of sensor array realization using approaches indicated in Figure 1.9. (a) Conducting polymer sensor array developed using approach A. (Reprinted with permission from Persaud et al. 2005. Copyright 2005 Oxford University Press.) (b) Microfabricated sensor array developed using approach B. Doped SnO2 films were deposited by pulsed laser deposition. Toper = 400°C. (Reprinted with permission from Aronova et al. 2003. Copyright 2003 American Institute of Physics.)


C) Microarray as a segmented sensing layer

1 2 3 4



High integration by simple separation of a monolithic metal oxide film into sensor segments; Sensor differentiation by temperature and membrane gradient.

Figure 1.11. Diagram illustrating approach to microarray fabrication proposed by Ehrmann et al. (2000).

odors) cause characteristic conductivity patterns to occur at the gradient microarray. An example of this approach realization is shown in Figure 1.12.

Figure 1.12. Micrograph of sensor microarray chip mounted in its housing. The chip contains four meander-shaped heating elements and a nanometer-thin SiO2 membrane on top of the metal oxide layer with a thickness gradient. Two thermoresistor meander beside the metal oxide film serve as temperature sensors to feed the heating control. Electrical contacts are provided by gold wire bonds. (Reprinted with permission from Ehrmann et al. 2000. Copyright 2000 Elsevier.) CONDUCTING POLYMERS
One of the early commercial e-nose systems used CP-based sensors, and they have been popular in much sensor array research. CP sensors have been found to respond to a wide range of organic vapors and operate at ambient temperatures with sensitivities of 0.1–100 ppm (De Wit et al. 1998). Compared with the metal oxides, organic polymers are much more diverse and can impart a wide variety of response characteristics to sensors. In the case of conducting polymers, the molecular interaction capabilities of a polymer can be selectively modified by incorporating different counter-ions during polymer preparation or by attaching functional groups to the polymer backbone. Another advantage of conducting polymers is that they can operate at room temperature (Albert et al. 2000). Examples of polymers used for design sensor arrays are given in Table 1.3.

Table 1.3. Examples of polymers used for sensor array design REFERENCE Kim et al. 2005; Ha et al. 2005 Carbon–polymer composites; siliconbased micromachined array of chemiresistive gas sensors 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. Poly(stylene-co-allyl alcohol) Poly(4-methylstyrene) Poly(caprolactone) Polystyrene–black–polyisoprene– black–polystyrene Cellulose acetate Poly(stylene-co-methyl methacrylate) Poly(styrene-co-butadiene) Poly(vinyl stearate) Hydroxypropyl cellulose Poly(butadiene) Poly(vinyl butyral)-co-vinyl alcoholco-vinyl acetate Ethyl cellulose Poly(vinyl acetate) Poly(4-vinyl pyridine) 1. 2. 3. 4. 5. 6. 7. Snopok and Kruglenko 2005 Polymer films; array of QCM-based sensors t-Bu-Calix-[6]arene t-Bu-Calix-[8]arene Pentacene Tetracene Phtalocyanine Dibenzotetraazaannylene Tetramethyl-dibenzotetraazaannulene

Breer et al. 1996

Electrochemical polymerization; array of chemiresistive sensors

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11.

Polypyrrole(PPy)-butane sulfonic acid PPy-PSA PPy-hexanesulfonic acid PPy-heptane sulfonic acid PPy-octane sulfonic acid PPy-decanesulfonic acid PPy-p-toluenesulfonic acid sodium salt PPy-p-toluenesulfonic acid monohydrate PPy-tetraethylammonium toluenesulfonate Ployaniline-NaHSO4 Poly(3-methylthiophene-tetraethylammonium tetrafluoroborate


Arrays of conductive polymer sensors are typically prepared electrochemically (Slater et al. 1993; Hodgins 1995b; Gardner and Bartlett 1995; Partridge et al. 1996). The electrochemical deposition of conductive polymers is reasonably controllable because films can be electrodeposited onto metalized areas and the film thickness can be varied by monitoring the total charge passed during the deposition process. The polymerization is usually carried out in a three-electrode configuration in which the working electrode is the sensor substrate. The electrodes are typically interdigitated electrodes or are a pair of metal leads separated by approximately 10–50 μm. The shortcomings of polymer-based technology are often long response times (20–140 s), inherent time- and temperature-dependent drift, poor batch-to-batch reproducibility, and a relatively high cost of sensor fabrication (Dickinson et al. 1998). The effects of humidity and sensor drift due to oxidation of the polymers over time are other disadvantages of polymers for sensor array fabrication (James et al. 2005), since they lead to instability of the sensory patterns. Microfabrication of large arrays of CPs with microscale dimensions are possible using interdigitated microelectrodes (Imisides et al. 1996; Stulik et al. 1994) created by photolithography (10-mm gap widths are not uncommon). And CP sensor arrays coupled with application-specific integrated circuits (ASIC) have been reported by Hatfield and co-workers (Hatfield et al. 1994; Neaves and Hatfield 1995) and by Gardner and co-workers (Cole et al. 2003; Garcia-Guzman et al. 2003). Additionally, CP arrays in e-noses have been used for monitoring the quality of foods and beverages. Conducting polymer–based e-nose technology also has been reported to offer a rapid, reproducible, and objective method for sewage odor assessment. Researchers have utilized electronic noses to monitor air quality in relation to the assessment of malodor in agriculture. The CP electronic nose has been successfully applied to several medical and veterinary science applications as well (Albert et al. 2000; Gardner, 2004). METAL OXIDE SEMICONDUCTOR SENSING TECHNOLOGY
Metal oxide semiconductors (MOS) have been used as gas-sensing elements since some of the earliest e-noses. Metal oxide sensors have fairly good sensitivity, particularly for polar analytes such as ethanol. Sensor selectivity can be shifted to different classes of compounds to some degree, either by changing the operating temperature of the sensors or by modifying the films by incorporating different amounts of noble-metal catalysts during the fabrication process (see Volume 4, Chapter 3, in this series). One drawback to metal oxide array fabrication is the necessity of incorporating a heating element to operate the array at high temperatures. Therefore, relatively high power levels are needed to run the sensors at elevated temperatures, and this is considered to be one of the primary drawbacks of these sensor systems. However, during the last decade, this problem was resolved. For example, AirSense Analytics (Schwerin, Germany) has introduced a multisensor element chip which allows considerable reduction in both the size and overall power consumption of a sensor array. Metal oxides also tend to be susceptible to “poisoning” by irreversible binding of sulfur-containing compounds and weak acids within a sample, as in cheese and vinegar (Dickinson et al. 1998). Despite these drawbacks, metal oxide sensors continue to be the most commonly used materials in the gas-sensing field (Albert et al. 2000; Romain et al. 2000; Mielle and Marquis 2001; Rock et al. 2008).


Figure 1.13. Optical micrograph of a 16-element micro-hotplate array (a) and a four-element suspended microhotplate array (b) with surface electrical contacts. [(a) Reprinted with permission from Taylor and Semancik 2002. Copyright 2002 American Chemical Society. (b) Reprinted with permission from Wheeler et al. 2007. Copyright 2007 American Chemical Society.)

The main advantage of MOX sensors is their potential for microminiaturization, which allows much diminished sizes and power consumption of devices. In this direction, considerable success was attained at NIST (USA) (Taylor and Semancik 2002; Wheeler et al. 2007; Meier et al. 2007). The electronic nose elaborated at NIST consists of eight types of sensors in the form of metal oxide film, deposited at the surfaces of 16 microheaters (Figure 1.13a) with two copies of each material. Precise heating control of individual elements, shown in Figure 1.13b, allows using them as a set of “virtual” sensors, working at various temperatures from 150 to 500°C, which increases the number of “virtual” sensors up to 5,600. The combination of sensitive films and the ability to change temperatures allows the device to act as an analytical equivalent of a nose with sensory neurons (Piggee 2008). Metal oxide sensor arrays have been used to detect a variety of different analytes under varying conditions. Three major groups of analytes for these arrays are toxic gases, volatile organic compounds (VOCs), and food-related species (Albert et al. 2000). ELECTROCHEMICAL SENSORS
Electrochemical sensors can also be used for electronic nose design (Stetter et al. 1986, 2001; Mari and Barbi 1992; Stetter and Penrose 1993). However, disadvantages such as the absence of sensors sensitive to specific gases, the lifetime of sensors, and difficulties related to integration and microminiaturization of electrochemical sensors limit their application in commercialized devices. These sensors are used mainly in the design of hybrid sensor arrays, or for designing an electronic nose aimed for a special application.


Figure 1.14. Sensor array consisting of eight CHEMFETs. (Reprinted with permission from Polk et al. 1999. Copyright 1999 Wiley.) MOSFET ARRAYS
There have been some attempts to design sensor arrays based on MOSFET sensors (Sundgren et al. 1990, 1991, 1992; Sommer et al. 1995; Albert et al. 2008). Arrays have been designed with from 2 to 12 MOSFET sensors. The actual design of the sensor array can vary significantly, depending on the application. Platinum, palladium, and iridium are the three most common catalytic metals used as gate materials in MOSFET sensor arrays. Palladium makes a good hydrogen sensor, while platinum and iridium have sensitivities for analytes such as ammonia and ethanol. As demonstrated by Polk et al. (1999), the CHEMFET sensor array also can be used for electronic nose design. A view of a CHEMFET-based sensor array is shown in Figure 1.14. A sensor array consisting of eight CHEMFETs was designed for simultaneous potentiometric and impedance sensing in the gas phase. The thickness of the transparent epoxy mask was 100 μm. However, due to low sensitivity to many gases, this type of sensor is used mainly for hybrid sensor arrays. MOSFET sensors have acceptable sensitivity only to hydrogen, ammonia, and ethanol. Much of the work with MOSFET cross-reactive arrays has been performed at the Linkoping Institute of Technology in Sweden. SAW SENSORS
The first application of pattern recognition methods to data from an array of quartz crystal microbalance (QCM) and surface acoustic wave (SAW) devices was in 1986 (Carey and Kowalski 1986; Ballantine et al. 1986). SAW sensors with polymeric covering find wide application in electronic nose elaboration today (Albert et al. 2000). Such distinctions as high sensitivity, the ability to work at room temperature, and low power consumption make sensors of this type very attractive for some application. Both the advantages and disadvantages of e-noses based on SAW sensor arrays are conditioned by the use of polymers.

The use of optical sensors for chemical sensing is widespread in many areas (see Volume 5, Chapter 6, in this series). In comparison to other sensor types, there is less information on the use of optical sensors in e-nose applications, but since the development of an optical e-nose system by the Walt group in 1996 (Dickinson et al. 1996; White et al. 1996), there has been a significant increase in utilization (Johnson et al. 1997; Sutter and Jups 1997; Bakken et al. 2001; Cho et al. 2001). Optical sensor systems resemble most closely classical sensor array systems, because the dimension of data output can be precisely defined and adapted (Dickinson et al. 1996; Suslick 2004; Suslick et al. 2004). Instead of having transduction principles based on electrical changes in resistance, potential, current, or frequency, the modulation of light properties is measured. In general, optical instruments are more complex but offer a variety of different measuring possibilities. The assortment of applicable technologies is high and ranges from diverse light sources over optical fibers to detectors such as photodiodes and CCD and CMOS cameras (Filippini and Lundstrom 2002). Therefore, various operating modes have been developed and deployed, using changes in absorbance, fluorescence, optical layer thickness, and polarization. For example, Walt’s group at Tufts University has constructed an optical system that interrogates the sensors at an (excitation) wavelength of 500 nm, and measures time and amplitude changes in fluorescence (emission) at 610 nm (Walt et al. 1998). They have explored the optical behavior of polymer beads with different surface chemistries, coated with a solvatochromic fluorescent dye (Dickinson et al. 1999). A solvatochromic fluorescent dye (one that is highly sensitive to the polarity of its local environment) is immobilized in different organic polymers to produce an array of diverse sensors (White et al. 1996). Changes in polarity of the dye’s surroundings induce characteristic shifts in the fluorescence emission spectrum, which can be monitored either at a single or at multiple wavelengths. In addition, the polymers used in this approach undergo a characteristic swelling as volatile compounds partition into the polymer matrix. A large number of different bead types are mixed together. They are attached to the ends of optical fibers, where each may be individually interrogated with a light pulse. The response of each sensor to absorbed vapors is thus based on both the mechanical swelling of the polymer layer and the spectral shifting of the entrapped dye. Because of the method in which the beads and fibers are assembled, the assignment of “sensors” (the sensitive polymer beads) to data channels (individual fibers) is random. A neural network is used to create an association between each sample type and the pattern of responses. In a real sense, this device resembles the structure and ontogeny of the mammalian olfactory sense more than many other realizations of electronic nose technology. This approach has led to the development of sensors that are fast (100 ms to 3 s response time), small (total array diameter 350 mm to 2 mm) (Dickinson et al. 1997), simple to fabricate, inexpensive, and can be made with a highly diverse set of coatings. The approach has been given the trade name of BeadArray and is being commercialized by Illumina, Inc. (San Diego, CA). Thus an array of fiber sensors can have wide-ranging sensitivities, a feature not easily obtainable with other sensor types. As with other types, differential measurements can also be used to remove commonmode noise effects. In their disfavor are the complexity of the instrumentation control system, which adds to fabrication costs, and their limited lifetime due to photobleaching. The fluorescent dyes are slowly consumed by the sensing process, the way sunlight bleaches fabric dyes (Kaplan and Braham 1998).


Figure 1.15. Colorimetric array responses for 18 common volatile organic compounds at saturation vapor pressure at 300 K. (Reprinted with permission from Suslick et al. 2004. Copyright 2004 MRS.)

Another unique variation on the electronic nose is the colorimetric sensor array recently proposed by Rakow and Suslick (Rakow and Suslick 2000; Suslick et al. 2004) for identifying solvent vapors. These authors noted that most odorous compounds have at least some Lewis base activity, and would bind to the central atom of a tetraphenylmetalloporphyrin, changing its color in a unique way. The authors spot a series of different metalloporphyrins onto a silica substrate in a stereotyped pattern and expose it to various solvent vapors. Each vapor produces a unique pattern of colors (see Figure 1.15). Such an “electronic nose” is not necessarily electronic, and does not even require an instrument. The authors, however, have proposed a CCD camera to reduce the array colors to digital form for processing by automatic means. The selectivity of the device is determined by the relative affinity of the volatile for the polymer. The lifetimes of these sensors, however, are presently limited by photobleaching processes. The optical format also requires the use of relatively sophisticated instrumentation, such as CCD cameras and precision optical components (Dickinson et al. 1998). OTHER SENSORS
The thermal sensor subtype of pellistors or calorimetric sensors have not been widely employed for e-nose systems, but some examples have been demonstrated (Gall 1993; Lerchner et al. 2000). There are also communications reporting gas sensor arrays for e-noses using cantilever-based sensors (Thundat et al. 1995) and capacitance-type sensors (Lonergan et al. 1996). For example, Dickert et al. have used an array of interdigital capacitors constructed from noble-metal electrodes to quantify solvent vapors based on the dielectric changes of different materials upon vapor incorporation (Dickert and Keppler 1995).

Each chemical sensor type has its own advantages for sensor array technologies and its own intrinsic problems. One solution to this problem is the use of more than one type of sensor in the array system; these systems are known as a hybrid e-noses (Holmberg et al. 1995; Ulmer et al. 1997; Mitrovics et al. 1998; Pardo et al. 2004; James et al. 2005). Gopel and co-workers (Gopel 1994; Mitrovics et al. 1998) made the observation that an e-nose that uses chemical sensors of several classes, i.e., sensors whose chemical principles are different, gives data that are more effective when comparing samples than simply increasing the number of sensors of a single class. Moreover, in large arrays of different sensors of one class, sensors that may not contribute information will always contribute noise (Zaromb and Stetter 1984). Experiments have shown that sensors with chemically independent responses are valuable and make the array more versatile and able to distinguish more analyte differences. Sensors of different classes generally provide more chemically different or chemically independent responses than sensors of the same class with small variations in their formula or structure (Mitrovics et al. 1998). Therefore, expanding the sensor array to make it heterogeneous in sensor class can lead to increased chemical independence of the sensor responses (Stetter et al. 1987). The use of different sensor classes, which respond to different physical or chemical properties of the analytes, allows larger numbers of sensors to be used, while still contributing information to the dataset. The major advantage with this type of e-nose is that it incorporates the advantages inherent in the different transducer technologies, also giving a choice for which chemical sensors should be used. The choice of chemical sensor will be dependent on the sample to be tested. The most common utilization of this system involves MOS and MOSFET sensors, but commercial systems are available that can use MOS, MOSFET, QCM, and AGS in various combinations. Electrochemical sensors also can be included in hybrid sensor arrays (Stetter et al. 2000). In particular, an e-nose designed by Stetter et al. (2000) utilized a sensor array formed by amperometric gas sensors (AGS), metal oxide (MOX) sensors, and piezoelectric quartz microbalance (QMB) sensors. At present we have information that hybrid sensor arrays have been designed using MOS, PC, electrochemical, MOSFET, and SAW sensors (Albert et al. 2008). Commercial electronic noses made by Alpha MOS (Toulouse), EEV Ltd. (Chelmsford, UK), Nordic Sensor Technologies AB (Linköping, Sweden), RST Rostock Raumfahrt und Umweltschutz GmbH (Rostock, Germany), and Lennartz Electronic GmbH (Tübingen, Germany) have used sensors of mixed type as well (Nagle et al. 1998).

The sampling system is usually sufficiently important that it is listed as the third essential component of an electronic nose (Mielle 1996). The role of the sampling system is to collect and convey the volatile sample to the sensors, then to restore previous conditions by means of a cleaning procedure. A good sampling system should both deliver a vapor sample to a sensor array in a reproducible way, and reduce sample-to-sample variation that might result from differences in humidity, temperature, or concentration. In addition, the purpose of the sampling system is to preprocess the sample in any way that increases the quality of the output data. This means that in order to obtain measurements with optimum


stability and reproducibility as well as high-amplitude signals and fast sensor response, the sampling device has to be designed in such a way that all factors capable of influencing sensor responses are optimized and kept under control, so that the only variable parameter is odor composition (Falcitelli et al. 2002). However, we have to note that not much research has been carried out on optimized sampling systems, even though some authors have demonstrated dramatic increases in performance of sensor arrays (Stetter et al. 2000). Some sampling systems also provide for automated measurement of a series of samples, although this is not a defining requirement. The most obvious use of a sampling system is to concentrate the vapors, in order to improve the sensitivity of the sensors (Schaller et al. 2000; Persaud et al. 2005). The purge-and-trap and solid-phase microextraction (SPME) techniques have already been used to improve the selectivity of the sensors. This latter method was successfully employed as a filter for ethanol (Aishima 1991; Privatet et al. 1998), that is, the ethanol contained in the samples was not adsorbed by the porous polymer material, and therefore was not delivered to the sensors. Consequently, the sensors were not blinded by the ethanol content and could response to other components. This approach was applied by Grate et al. (1993) in a four-SAW sensor device which was optimized for chemical warfare agents. It was later commercialized for hydrocarbon measurement by H. Wohltjen at Microsensor Systems, Inc. A short tube of organic sorbent (Tenax) was used to absorb vapors from the air. These were desorbed using a heater and passed through a short GC column to the sensor array. Similar preconcentrator approaches have been used by other workers as well (Strathmann et al. 2001). Concerning the length of analysis time, it is important to state that sample throughput is related not only to acquisition, but also to the sampling time, headspace equilibration time, and recovery or cleaning time (Mielle and Marquis 2000). For e-nose and MS-based systems, the main part of the analysis time is spent in equilibration. However, the total analysis time may be reduced by using a pipeline mode for the sampling: A new sample equilibrates during the analysis of the current sample. Recovery time for a sensor array system is related to the sensor type and to the nature of the compounds adsorbed. It can last up to 40 min for some low-volatility compounds (Wunsche 1995). The use of an autosampler reduces the acquisition and mainly the recovery time, even at relatively low concentrations, by reducing the amount of volatile reaching the measurement cell. But this also dramatically reduces the sensor response (Lacoste 1999). However, it was shown that, through optimization of the sampling system and measurement cell, the cycle time could be reduced to less than 10 min, retaining high measurement accuracy and low noise level, over a large concentration range (Mielle and Marquis 1999, 2000). The small overshoot was due to a small unbalanced flow rate between the baseline and the sampling period. Samples often contain substances that are common to all, and although the sensors are dominated by them, they do not contribute to discrimination. In bacterial cultures, for example, the common substance is water. In beer and wine, water and alcohol will be present in all samples in much larger quantity than any other constituent. McEntegart et al. (2000) used Nafion tubing and anhydrous sodium sulfate to remove selectively water, alcohol, and some other hydrophilic vapors from samples. Although sensor signals, on average, were reduced by a factor of 10 or more, the removal of the dominant constituents greatly improved selectivity. Another type of sampling system (Stetter et al. 2000) allowed TNT adsorbed to silica sand to be detected and discriminated from structurally similar compounds by vaporization of a sample from a tiny beaker, using a hot platinum filament. A second filament was located


downstream to combust the sample to electrochemically reactive compounds, probably nitrogen oxides and carbon monoxide. The measurement chamber also plays an important role in the sampling process (Lezzi et al. 2001; Falcitelli et al. 2002). Nonadsorbent and inert materials have to be selected with care to avoid memory effects. The choice of the material has a remarkable effect on the chamber projecting, as unsuitable mechanical properties can hamper refined machining and complex design. Glass and fused silica, for example, are mainly processed as craft work, while stainless steel is very hard to machine on a small scale using common techniques. Polytetrafluoroethylene (PTFE) is soft enough to be machined easily, but, for this same reason, its mechanical properties make it difficult to craft into small components. Moreover, it is microporous and so acts as a polymer trap, so attention has to be paid during use to avoid contaminations and memory effects. All these materials can be treated with aggressive solvents and dried in an oven at high temperatures, even if in the case of Teflon it is suggested not to exceed 200°C. The volume of the chamber has to be properly dimensioned for any range of gas flow rates, in order to obtain a homogeneous flow with a low-speed gradient with no recirculating zones or stagnant regions. It is also important that all the sensors are exposed at the same time to the same odor concentration, so that their performances will not be related to their position inside the chamber. Several useful advances related to optimization of measurement chamber have been described by Falcitelli et al. (2002).

Like the mammalian olfactory system, the electronic nose uses a holistic approach to distinguish aromas. It does not separate or attempt to identify the individual chemicals responsible for the pattern. The electronic nose works equally well on pure compounds or on undefined samples such as flavors, aromas, and other complex odors. Conventional reductionist analytical methods often become less reliable as sample complexity increases. Some work on grain odors, for example, was preceded by a 3-year effort by the U.S. Department of Agricultre (USDA) to use GC-MS to distinguish grain quality. The author of the final report on this study stated, after analysis of more than 300 samples, that “no relationship between the chemical composition and the odor could be found” (Weinberg 1986). Other authors have had similar problems correlating the results of detailed chemical analysis with organoleptic responses (Schaller et al. 1998; Zhou et al. 1999). Another problem of human testing panels backed by gas chromatography and mass spectrometry is connected with fact that those methods are time-consuming, expensive, and seldom performed in real time in the field (Kaplan and Braham 1998; Zou and Zhao 2008). Electronic noses have the ability to perform sensory-based analyses such as for odor/aroma and taste rapidly and in a cost-efficient manner. This new technology offers the possibility of arranging for continuous real-time monitoring of odor at specific sites in the field over hours, days, weeks, or even months. An electronic device can also circumvent many other problems associated with the use of human panels. Individual variability, adaptation (becoming less sensitive during prolonged exposure), fatigue, infections, mental state, subjectivity, and exposure to hazardous compounds all come to mind (Kaplan and Braham 1998). Not only are the electronic systems more rapid and objective than human testing panels, they are much more amenable to routine use, for example, in production QC applications. Since they correlate


well with human sensory panels, the instruments can be described as a “consumer-based instrumental test.” Electronic noses also correlate well with more classical analytical methods such as HPLC and GC/ GC-MS instruments which measure a specific analyte or group of analytes (Tan et al. 2001). However, e-noses are much faster. For example, HPLC analysis of caffeine levels in a carbonated soft drink generally takes about 15 min. An e-tongue will give the result in approximately 3 min. High sensitivity is other advantage of e-noses. Electronic noses are often even more sensitive than the human nose (see Table 1.4). There is some evidence that sensors differentiate aromas on the basis of relatively few compounds, and in the future a relationship between specific chemicals and a single

Table 1.4. Detection threshold levels of human olfactory systems and electronic noses

REPORTED HUMAN ELECTRONIC NOSE TYPE OF ELECTRONIC THRESHOLD (ppm) THRESHOLD (ppm) NOSE 7–17 (b) 0.4–10 (b) (4–15) × 10−3 (b) (10–50) × 10−3 (2–50) × 10−3 (20–40) × 10−6 (b) 0.2–7 3–9 7–13 13–30 20–50 0.13–1.3 0.2–1.3 0.7 5–25 <1 (50–100) × 10−3 (10–50) × 10−3 (10–50) × 10−3 (50–100) × 10−6 <0.2 0.6 <2 <10 40 <0.06 0.3 – – + 1.3 2 3 – + + – – – Fox 3000 (12 MOS) Fox 3000 (12 MOS) Fox 3000 (12 MOS) Fox 3000 (12 MOS) Fox 3000 (12 MOS) Fox 3000 (12 MOS) 20 CP composite 20 CP composite 20 CP composite 20 CP composite 20 CP composite 20 CP composite 20 CP composite Aromascan (32 CP) Fox 3000 (12 MOS) 6 Taguchi (SnO2) 20 CP composite 20 CP composite 20 CP composite Aromascan (32 CP) Fox 3000 (12 MOS) 6 Taguchi (SnO2) Aromascan (32 CP) Fox 3000 (12 MOS) 6 Taguchi (SnO2)

REFERENCE Stetter et al. 2000 Stetter et al. 2000 Stetter et al. 2000 Stetter et al. 2000 Stetter et al. 2000 Stetter et al. 2000 Doleman and Lewis 2001 Doleman and Lewis 2001 Doleman and Lewis 2001 Doleman and Lewis 2001 Doleman and Lewis 2001 Doleman and Lewis 2001 Doleman and Lewis 2001 Hudon et al. 2000 Hudon et al. 2000 Hudon et al. 2000 Doleman and Lewis 2001 Doleman and Lewis 2001 Doleman and Lewis 2001 Hudon et al. 2000 Hudon et al. 2000 Hudon et al. 2000 Hudon et al. 2000 Hudon et al. 2000 Hudon et al. 2000

Ethyl acetate (a) Butyric acid (a) Diacetyl (a) n-Hexanal (a) Methional (a) Furanol (a) n-Nonane (c) n-Octane (c) n-Heptane (c) n-Hexane (c) n-Pentane (c) 1-Pentanol (c) 1-Butanol (c) 1-Butanol (d) 1-Butanol (d) 1-Butanol (d) 1-Propanol (c) Ethanol (c) Methanol (c) Acetone (d) Acetone (d) Acetone (d) Ethanethiol (d) Ethanethiol (d) Ethanethiol (d)

0.9–1.9 5–500 13–600 141

0.1 × 10−3

(+), Detected at the same concentration as submitted to human noses; (–), not detected (when response <3× background noise) at the same concentration as submitted to human noses; (a), concentration in water; (b), orthonasal analysis; (c), concentration in air; (d), concentration in vapor in equilibrium with a liquid phase at 22.5–25°C. Source: Reprinted with permission from Ampuero and Bosset 2003. Copyright 2003 Elsevier.


flavor attribute may be achievable. Also, the possibility exists to differentiate between “top” and “middle” notes of aroma. In addition, the “odor/aroma fingerprint” could then be stored in a database in a way analogous to the memorization of olfaction perception in the human brain.

Limitations to utilizing the full potential of electronic noses include loss of sensitivity in the presence of high concentrations of a single component such as alcohol; the inability to provide absolute calibration; the relatively short lifetimes of some sensors; the necessity for considerable method development work for each specific application; and an inability to obtain quantitative data for aroma differences (Harper 2001). Electronic noses are intended to detect odorous compounds, but it is not always clear that discriminations are based on odorous rather than nonodorous, and possibly incidental, components of the headspace. The drift of output parameters is another problem for e-noses (Zubritsky 2009). All e-noses are subject to drift, but the problem has received the most attention in the resistive sensor instruments. In particular, drift falls into two categories: sensor drift, which is due to the aging or degradation of individual sensors; and system drift, which encompasses all sensors. Some e-noses are designed to monitor both kinds of drift so that users know when sensors need to be replaced. In some instruments, individual sensors can be replaced, but in others, the entire array must be replaced. In all cases (except optical sensors), the e-nose must be retrained afterward. However, it is necessary to take into account that in some cases the “drift” is a consequence of the sensor environment instability. For example, if you put a metal oxide–based e-nose into a room where CO and ozone levels fluctuate dramatically, the variations may register on the instrument. Some people consider these variations as drift, but, strictly speaking, they are not drift. Related to drift is the issue of an e-nose’s sensitivity to humidity. Humidity is a known problem, especially with polymer-based sensors, and care needs to be taken in their use (James et al. 2005). For example, Kaplan and Braham (1998) showed that an e-nose lost sensitivity in the presence of water vapor. This complicates the detection of volatile odors in the presence of high levels of water vapor. Research found that e-noses based on hydrophilic conducting polymers are the most prone to this problems. Therefore, when humidity levels are not compensated for or controlled, it is possible that the humidity is responsible for some successful discriminations. Therefore, minimizing the impact of humidity is a key task for any e-nose designer. Two companies, at least, are addressing this problem. Some instruments are capable of choosing either an ambient air reference (when the humidity is varying) or a filter to remove humidity (when the level is relatively constant). For example, Bloodhound Sensors is developing systems based on discotic liquid crystals, which have very low response to water vapor. Alternative sensor types, described as water-insensitive chemoresistors, are being developed by Marconi Advanced Technologies. Reproducibility is another common and important problem with e-noses (Zubritsky 2009). One reason that it is difficult to get consistent responses is that sensor materials age or become “poisoned” by some chemicals. In fact, the lifetimes of sensor materials can range from several months to 1 or 2 years, depending on the underlying chemistry and the sensor’s environment. The second reason is variations in


sampling. To compensate for variations in sampling, some e-noses use auto-sampler systems that control the temperature, shake the samples, and perhaps equilibrate the headspaces. Although this yields better reproducibility, these systems can be large and expensive. However, some companies have put a lot of effort recently into miniaturizing sampling systems.

As noted earlier, the first commercial electronic nose devices were launched in the 1990s. Among the first were systems from Alpha MOS in 1993, Neotronics and Aromascan in 1994, and Bloodhound Sensors and HKR Sensorsysteme in 1995. Since then, many companies worldwide have started manufacturing electronic nose instruments, using many different detection principles and sensor types, so that many electronic nose systems are available on the market today, including those listed in Table 1.5. Each detection method has advantages and drawbacks, so companies are increasingly configuring their products to include several measuring principles in one instrument. For example, Alpha MOS is developing instruments (see Figure 1.16) that include fingerprint mass spectroscopy with the more traditional metal oxide sensor arrays. Lennartz ( and Marconi Advanced Technologies ( have integrated quartz crystal microbalance sensors with metal oxide semiconductors, which have been used in parallel with GC-MS and human sensory panel sniff tests to monitor “off” odors from food packaging materials. A similar array, but with conducting polymer chemoresistors also incorporated, has been used with some success to monitor amniotic fluid leakage in expectant mothers. Applications of commercial e-nose devices range from quality control to landmine detection, from security controls to health screening. Most of the machines listed in Table 1.5 are priced from $20,000 to $100,000 (U.S.), but prices should drop in a few years as competition heats up and sensor technology improves. Most models now on the market are fairly large, none-too-portable, lab-type systems (see Figure 1.16), but several manufacturers have said they are working on miniaturized versions. Low-cost miniaturized devices for personal use are already beginning to emerge on the market. One example of such a miniaturized instrument is shown in Figure 1.17. The Cyranose 320 requires a one-time training session in which the user exposes the sensor to each type of sample that will be encountered during testing, creating a base-group to which all future samples will be compared. The sampling step involves placing the tip of the device near the sample and simply pressing “Run.” Air referencing, vapor sampling, sensor measuring, and data processing are all handled automatically and take roughly 1 min to complete. If the sample matches one of the pretrained samples, the unit reports the identity of the sample. If the unit does not recognize the sample, an “Unknown” reading is given. The unit automatically resets itself, and the polymer composite sensors return to their original resistance. This real-time, portable device enables food companies to spot-test raw materials for batch-to-batch consistency, spoilage, or contamination. The Cyranose 320 is also used by chemical and petrochemical companies for quick assessment of the chemical status associated with various industrial processes. For example, profiling a chemical environment in a hazardous materials situation allows emergency crews to accurately select fire retardants, containment strategies, and protective gear. The device weighs 0.91 kg, and response time is less than 1 min.

Table 1.5. Commercially available electronic nose instruments


Fi Fr Se 32 14 32 8–28 1 — 6 8–40 22 Laptop Desktop UK UK US UK US US Ge Ge Ge US Se UK Ge Ge US Desktop Laptop Palmtop Desktop Desktop Desktop Desktop 6–24 2 Desktop

Airsense Airsense Agilent Analysis GmbH Draeger Environics Smith Group Alpha MOS-Multi Applied Sensor Orhanoleptic Systems AromaScan PLC Bloodhound Sensors Ltd. Cyrano Sciences Inc. EEV Ltd. Chemical Sensor Systems Electronic Sensor Technology Inc. Hewlett-Packard Co. HKR-Sensorsysteme GmbH Agilent Technology Lennartz Electronic GmbH Microsensor Systems Nordic Sensor Technologies AB


Marconi Applied RaeSystemes RST Rostock Raumfahrt undImweltschatz GmbH Sysca AG Sawtek Inc. Technobiochip MOS SAW QCM

38 2 8


CP, conducting polymer; MOS, metal oxide semiconductor; IR, infra red; SAW, surface acoustic wave; QCM, quartz crystal microbalance; QMS, quadrupole mass spectrometry; GC, gas chromatography; FET, field effect transistor; IMS, ion mobility spectrometry.


Figure 1.16. Fox electronic nose manufactured by Alpha MOS, France. This unit requires a PC to run the system. (Uploaded from

Figure 1.17. View of Cyranose 320 portable electronic nose designed by Cyrano Sciences, Inc., of Pasadena, California, using an ingenious technology licensed from Caltech. Nanocomposite sensor array includes 32 CP-based sensors. (Uploaded from Cyranose_320.php.)


Figure 1.18. Electronic nose installed at ISS in 2008. (Uploaded from

An electronic nose based on a polymer sensor array is shown in Figure 1.18. It has was developed by the Jet Propulsion Laboratory of the California Institute of Technology. Its weight does not exceed 4 kg, and the mass of the sensor unit is only 840 gr. It includes a sensor array consisting from 32 sensors. This e-nose is able to analyze air by itself and then send data to an external computer. Sensitivity of the sensors can be tuned to the parts-per-billion level. Power consumption is only 20 W. In 2008 this device was installed on the International Space Station (ISS). Another version of an electronic nose using a polymer sensor array is shown in Figure 1.19. A portable electronic nose system based on a laptop PC or PDA has been developed and demonstrated successful differentiation between the complex real samples, i.e., brandy and whiskey. This

Figure 1.19. Portable electronic nose system based on a carbon black–polymer composite sensor array. (Reprinted with permission from Kim et al. 2005. Copyright 2005 Elsevier.)


system, based on an array of 12 chemiresistive sensors, consists of the hand-held sensing module with vapor delivery components, a single sensor array chip and signal conditioning circuitry, and the personal digital apparatus with the function of processing measured signals, such as data acquisition and pattern recognition. A key part of this e-nose system is the sensor array chip, which is fabricated using Si bulk micromachining and carbon black–polymer composite sensors. An electronic nose based on a metal oxide sensor array is shown in Figure 1.20. The KAMINA device, developed at the Karlsruhe Research Center (FZK), is comprised of a microarray chip (only some mm2 in size), fluidic components for gas sampling, and the entire microprocessor-controlled operating electronics in a single unit. Gas sampling can be optionally configured. There are several options for gas guidance (particle filter, tubes of stainless steel, gold-plated stainless steel, or glass). Further, several sampling options are available (ventilator, micropump, or no sampling arrangement) that, where required, allow adjustment of the gas flow. The part of the device below the microarray chip contains the complete controlling measuring electronics as well as the regulated heating supply for the four chip heaters. The operating electronics control each of the four heating meanders individually, to maintain a temperature gradient across the microarray that is responsible for differentiation of the gas selectivity between the individual sensor segments. This temperature gradient is kept constant with the aid of two temperature sensors (Ehrmann et al. 2000). (This approach to sensor array fabrication was discussed in Section 5.2.2.) The gas sensor array consists of 38 or 16 sensor segments. It can be fabricated using Si/ SiO2 or Al2O3 substrates and SnO2 or WO3 gas sensing layers. A standard serial data interface provides the communication to the controlling PC. A power supply unit for either 230-V or 110-V connection, as well as a 12-V or 24-V inverter, are available. Nearly all gases except for nitrogen and rare gases can be detected, often at very low concentrations, e.g., less than 1 ppm. An electronic based on an array of electrochemical sensors is shown in Figure 1.21.

Figure 1.20. Operating device of the Karlsruhe Micronose KAMINA with the head cover lifted. (Uploaded from and


Figure 1.21. Prototype of EC sensor module for the Lennartz electronic MOSES II EN system. Beside it is an EC (amperometric) gas sensor made by TSI, St. Paul, Minnesota. (Reprinted with permission from Stetter et al. 2000. Copyright 2000 Elsevier.)

Odor is very important in food, beverage, pharmaceuticals, and personal care industries, so one can expect maximal application of electronic nose in these fields. The expectations of consumers regarding the quality of products in these fields are continually increasing as a result of a greater range of choices in the marketplace together with targeted advertising, which emphasizes product quality. Competition for market share and the added emphasis on quality have increased pressure on product development and rigorous quality control to meet consumer expectations. Due to their simplicity, rapidity, and objectivity, electronic noses can be incorporated into instruments aimed for quality control, product matching, origin identification, spoilage detection, and flavor quantification. A particularly potent example is coffee, where the simplest electronic noses can make fine distinctions between blends (Gardner et al. 1992). Vintners have been able to identify wines by provenance as well as vintage (Guadarrama et al. 2000; Marti et al. 2005; Berna et al. 2008). Just like a human taster and odor controller, e-noses can be used for both quantitative and qualitative applications. Quantitative applications include sensory score correlation and the measurement of the concentration of flavors or fragrances within a food or cosmetic product. Qualitative sensory applications include the determination of the origin and quality of raw materials and consistency of finished products (Tan et al. 2001). Electronic noses can be applied by food manufacturers to such tasks as freshness testing, quality control, and screening of incoming raw materials, not to mention feedback control to optimize bioreactors and minimize batch variation, and monitoring for accidental or


intentional contamination or mislabeling of manufactured food products (Kaplan and Braham 1998). Electronic nose systems are well suited to comparing final products to reference standards, even replacing human taste panels in some applications. Testing of food freshness is especially important for the elderly, since the senses of taste and smell dull with advancing age (Gomez et al. 2006) (see Table 1.6). Other applications of the electronic nose technologies include shelf-life measurements and the evaluation of interactions between packaging and product. In addition to this field, e-noses can be used in other areas such as petroleum qualitative and quantitative analysis, detection of explosives, classification and degradation studies of olive oils, development of a field odor detector for environmental applications, quality control applications in the automotive industry, discrimination between clean and contaminated cows’ teats in a milking system, cosmetic raw materials analysis, plus many other important areas such as medicine and space exploration (Baby et al. 2000; Gardner et al. 2000; Morvan et al. 2000; Tan et al. 2001). Electronic noses may be used to analyze breath, sweat, urine, and stools, and possibly diagnose some illnesses as a result; work in this area has been done at companies such as Aromascan, Bloodhound Sensors, and EEV Chemical Sensor Systems (Kaplan and Braham 1998). Thus, an electronic nose could help solve problems in many fields, including health care, environmental monitoring, indoor air quality, safety and security, and the military (Kaplan and Braham 1998; Scorsone et al. 2006).

Table 1.6. Some reported applications of electronic noses in the food industry
FOOD Seafood (oyster, sardine, etc.) Fish (cod, haddock) Fish Fish Fish (trout) Grains Ground pork/beef Boar Sausage Food flavours (orange, etc.) Wheat Wheat and cheese Tomatoes Cheese Cheese

TEST Freshness Freshness Freshness Freshness Freshness Classification Discriminate and effect of ageing Taints in meat Meats discriminate Flavor identification Grade quality Discriminate and ageing Effect of irradiation and stress Maturity of cheddar Discriminate

SENSORS/TYPE REFERENCE 1/MOSa 4/MOS 1/MOSa 6/MOS 8/EC 15/mixed 15/mixed 14/MOS 6/MOS 8/BAW 4/4rEC 20/CP 7/mixed 20/CP 8/CP Nanto et al. 1991 Olafsson et al. 1992 Egashira et al. 1994 Barbi et al. 2007 Schweizer-Berberich et al. 1994 Winquist et al. 1993 Bourrounet et al. 1995 Tan et al. 1995 Nakamoto et al. 1993 Stetter et al. 1993 Pisanelli et al. 1994 Winquist et al. 1995 Persaud and Travers 1997

Not strictly an electronic nose as defined here, but an odor monitor.

MOS, metal oxide semiconductor; EC, electrochemical; BAW, bulk acoustic wave; CP, conducting polymer. Source: Adapted with permission from Gardner et al. 2000. Copyright 2000 Elsevier.


In recent years there has been great progress in elaboration of the principles of electronic nose functioning, as well as in commercialization of attained results. Electronic noses are available on the market, and even now allow resolving a wide range of tasks in various areas. However, in spite of the considerable progress, the electronic nose as a commercial device has not reached its full potential. There are still problems with rate of response, stability, and portability. However, the appearance of new materials, elaboration of modern technologies, and development of mathematical methods of information processing offer hope of the appearance in the near future of new devices with much better functional parameters. However, it is hard to expect that multifunctional devices without application limitations will appear in the near future. A single instrument that could be used in every possible application would be overly complicated due to the large number of sensors and time-consuming statistical analysis. Therefore, in our view, the trend toward creating systems for specific applications is well founded. It is necessary to note that the presence of analytical instruments for gas analysis based on such methods as chromatography and mass spectroscopy does not limit development of the electronic nose market, because devices are designed for different tasks (Mielle and Marquis 2000; Marti et al. 2005). The higher-cost instruments based on traditional analytical methods such as GC or MS analysis, operated by skilled laboratory workers, will always be needed to determine qualitatively or/and quantitatively why one food sample differs from others. The electronic nose is better adapted for such tasks as quick quality tests in various applications, routine work, or in cases where nonodorous or irritant gases need to be detected. There are a number of application areas where the possibilities are extremely good. Using such intelligent sensing systems is a key factor in the modernization of industry and in protection of the environment (Snopok and Kruglenko 2005). In some cases, where online use and portability are requirements, gas sensors have clear advantages over the GC- and MS-based instruments as well. Portable, application-specific devices could be used for a wide range of tasks (Kaplan and Braham 1998). The reduced need for flexibility would allow more user-friendly operation, so that, for example, environmental field workers, car mechanics, and doctors could find an extra tool in their armories. Similar instruments could also be incorporated into in-process control systems, reducing the time and cost of analyzing samples offline and minimizing waste.

G. Korotcenkov is thankful to the Korean BK21 Program for support of his scientific research.

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